Resin particle and process of producing the same

ABSTRACT

Provided is a resin particle comprising a resin (a) and a filler (b) contained in the particle; the particle has a volume average particle diameter of from 0.1 to 300 μm and a shape factor of from 110 to 300; the particle has an outer shell layer (S) comprising at least a portion of the filler (b); the layer (S) is at least 0.01 μm thick and has a thickness that is ½ or less of the maximum inscribed circle radius of the particle cross section. When used as a toner resin, it is excellent in blade cleaning properties and wide in the fixation temperature range; when employed as a paint additive or a cosmetics additive, it is excellent in masking properties; when used as paper coating additive, it is excellent in ink retention; when utilized as an abrasive, it is excellent in abrasion.

CROSS REFERENCE TO RELATED APPLICATION

The present application is a 35 U.S.C. §371 national application ofPCT/JP2004/010056 filed Jul. 14, 2004, which is incorporated herein byreference in its entirety.

TECHNICAL FIELD

The present invention relates to resin particles, and more particularlyto resin particles valuable for toners used for electrophotography,electrostatic recording, electrostatic printing, etc, paint additives,cosmetics additives, paper coating additives, abrasives, slush moldingmaterials, hot inlet adhesives, powder paints, other molding materials,and the like.

BACKGROUND ART

Resin particles are conventionally known that are produced bydispersing, in an aqueous medium, a resin solution in which the resinwas dissolved in a solvent in advance in the presence of a dispersing(assistant) agent such as a surfactant or water-soluble polymer, andthen removing the solvent via heating, pressure reduction, or the like(the solution resin suspension process). The shapes of these resinparticles obtained by the solution resin suspension process aredifficult to be regulated, and in general they have a spherical form.

Use of the spherical particles as a paint additive or a cosmeticsadditive leads to insufficient masking properties in some cases. Whenthe particles are used as a paper coating additive, the retention of inkis sometimes poor due to lack of oil absorbance. When the particles areused as an abrasive, the frictional resistance is small, therebygrinding properties are poor in some cases. The use of the particles asa toner resin poses the problem of rendering cleaning propertiesinsufficient when the toner remaining on a photoreceptor without beingtransferred to a paper surface is cleaned with a blade. For solution ofsuch problems, a process is available that involves appropriatelyelasticizing the surfaces of particles prior to volume shrinkage of theparticles with a solvent-removing, and making smaller the surface areadecreasing speed than the volume shrinking speed to form resin particleshaving unevenness on the surfaces. As a means of rendering the surfaceof a particle to be elastic is proposed a method of forming a shellmaterial on the resin particle surface by means of interfacialpolymerization or in-situ polymerization (refer to Japanese PatentApplication Laid-Open No. 4-209630). This method, however, does notsufficiently exhibit properties required for the particles due to theeffect of the shell material. For instance, a toner in this case causesthe problem of lowering low-temperature fixing properties and anti-hotoffset properties, thereby extremely narrowing the fixing temperaturerange.

DISCLOSURE OF THE INVENTION

Problems to be Solved by the Invention

The present invention was made in consideration of the above situationsin the prior art. More specifically, the present invention is directedto the provision of a resin particle that is excellent in maskingproperties when being used as a paint additive or a cosmetics additive,is excellent in retention of ink when being used as a paper coatingadditive, is excellent in abrading properties when being used as anabrasive, is excellent in blade cleaning properties, and wide in fixingtemperature range when being used as a toner resin.

Means by which to Solve the Problem

The present inventors have diligently studied to attain the aboveobject, leading to the present invention.

In other words, the present invention includes a resin particlecomprising a resin (a) and a filler (b) contained in the particle; theparticle has a volume average particle diameter of from 0.1 to 300 μmand a shape factor (SF-2) of from 110 to 300; the particle has an outershell layer (S) comprising at least a portion of the filler (b); thelayer (S) having a thickness of at least 0.01 μm and the thickness being½ or less of the radius of the maximum inscribed circle of the crosssection of the particle.

In addition, the invention includes a process of producing the aboveresin particle; the process involves (1) dispersing in an aqueous medium(W) a filler-containing dispersion liquid (D) produced by dispersing thefiller (b) in a dispersion liquid (D0) comprising the resin (a) and/orits precursor (a0) in a solvent (s), forming an oil-in-water dispersionliquid (D1), thereby forming in an oil drop (A0) an accumulated layer(S0) comprising at least a portion of the filler (b), and (2) removingthe solvent of the oil-in-water dispersion liquid (D1) to obtain a resinparticle (A).

EFFECT OF THE INVENTION

A resin particle of the present invention shows the following effects:

-   [1] excellent in masking properties.-   [2] excellent in oil absorbing properties.-   [3] excellent in abrasive properties when being used as an abrasive.

In particular, when the resin particle is used as a resin particle for atoner, it exhibits the following effects:

-   [4] good in blade cleaning properties.-   [5] excellent in low-temperature fixing properties.-   [6] excellent in anti-hot offset properties.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a sectional schematic diagram of a resin particle of thepresent invention; the particle has an outer shell layer thickness (T).

FIG. 2 is an SEM image of resin particles obtained in Example 2.

FIG. 3 is a TEM image of a resin particle obtained in Example 2.

FIG. 4 is an SEM image of resin particles obtained in ComparativeExample 1.

FIG. 5 is an SEM image of resin particles obtained in Example 7.

FIG. 6 is a TEM image of a resin particle obtained in Example 7.

FIG. 7 is an SEM image of resin particles obtained in ComparativeExample 4.

BEST MODE FOR CARRYING OUT THE INVENTION

A resin particle [hereinafter, also referred to as (A)] of the presentinvention includes a resin (a) and a filler (b) and has an outer shelllayer (S) comprising at least a portion of the filler (b) [hereinafter,of the filler (b), a filler forming the outer shell layer (S) is alsoreferred to as (b*)]. Inclusion of a filler (b) is indicative of thestate of a filler (b) being present underneath the surface or inside theresin particle (A), and is capable of being observed by a transmissionelectron microscope (TEM). When a filler (b) is exposed to the outsideof the resin particle (A), or is adsorbed on the surface of the resinparticle (A), with respect to the surface and the bulk properties of theresin particle (A), the properties of the filler (b) are dominant, andthus the properties of a resin (a) are rarely exhibited. Conversely,when a filler (b) is contained inside the particle, the properties of aresin (a) is readily expressed. In other words, a resin (a) is presenton the surface of the resin particle (A) and further also in the insideof the outer shell layer (S), as described later, formed by a filler(b*) is present a portion occupied by a resin (a), therefore thelow-temperature fixing properties are good particularly when used as atoner resin particle. In addition, where a wax is contained in the resinparticle (A), in thermal fixing, the wax oozes on the resin particle (A)surface from the portion occupied by the above resin (a), so theanti-hot offset property is good.

Additionally, the thickness of the outer shell layer (S) comprising atleast a portion of the filler (b) formed adjacent the surface of a resinparticle (A) of the present invention can be determined by imageanalyzing the image of the cross section of the resin particle by meansof a transmission electron microscope (TEM).

That is, the process involves dispersing resin particles in a saturatedsucrose solution (67% by mass solution; % is by % by mass, unlessotherwise indicated), freezing the resulting solution at −100° C.,slicing it with a cryomicrotome in a thickness of about 1,000 angstroms,staining the filler (b) containing (b*) by means of rutheniumtetraoxide, and subsequently photographing the cross sections of a resinparticle under a transmission electron microscope at a magnification of10000 times to determine the thickness of the outer shell layer of afiller (b*) using an image analyzer [e.g., nexus NEW CUBE ver. 2.5(manufactured by NEXUS), or the like]; the thickness of the outer shelllayer is the maximum distance (T), where the area of a filler (b)primarily including a filler (b*) is 50% or more on an area of a portionof a thickness of a certain distance taken from the resin particlesurface to a vertical direction toward the particle inside, for thecross section of the maximum cross-sectional area. Additionally, theabove measurement value is an average value obtained by averaging thevalues of 10 resin particles randomly selected. FIG. 1 indicates anexample of (T).

Moreover, distinguishing between the outer shell layer (S) and the resin(a) is difficult in the observation of a TEM image, an outer shell layerthickness (T) can be determined by mapping a resin particle crosssection obtained by the above method using an apparatus escapable ofcomposition mapping (e.g., an energy dispersive X-ray spectroscopyapparatus (EDX), an electron energy loss spectroscopy apparatus (EELS),and the like), specifying the outer shell layer (S) from the compositiondistribution images obtained from the analysis, and using the abovemethod.

The lower limit of the thickness of the outer shell layer of a filler(b*) is normally 0.01 μm, preferably 0.02 μm, more preferably 0.03 μm.The upper limit of the thickness of the outer shell layer is normally ½of the radius of the inscribed circle of a resin particle (A),preferably ⅓, more preferably ¼, most preferably ⅕. To allow the shapefactor (SF-2) of the resin particle (A) to fall within the range asdescribed later, the surface area decreasing speed needs to be extremelydecreased as compared with the volume shrinking speed during volumeshrinkage of the resin particle (A), and it is important to properlyelasticize the resin particle surface, thereby increasing the viscosityof the resin particle surface compared to the resin particle inside. Ifthe thickness of the outer shell layer of the filler (b*) is within theabove range, the difference of viscosity between the resin particlesurface and the resin particle inside is increased, readily allowingunevenness to appear on the particle surfaces.

The volume average particle diameter of a resin particle (A) is normallyfrom 0.1 to 300 μm from the standpoint of particle diameter uniformity.The upper limit is preferably 200 μm, more preferably 100 μm,particularly preferably75 μm, most preferably 50 μm; the lower limit ispreferably 0.2 μm, more preferably 0.3 μm, particularly preferably 0.5μm, most preferably 1 μm. If the volume average particle diameter isless than 0.1 μm, the effect of unevenness of the particle surface isdecreased; if it exceeds 300 μm, the uniformity of the particle diameteris difficult.

In particular, when the resin particle is used as a toner, the volumeaverage particle diameter of a resin particle (A) is normally from 3 to10 μm. The upper limit is preferably 9 μm, more preferably 8 μm,particularly preferably 7 μm, most preferably 6.5 μm; the lower limit ispreferably 3.5 μm, more preferably 4 μm, particularly preferably 4.2 μm,most preferably 4.5 μm. If the volume average particle diameter is 3 μmor more, the transfer to paper and blade cleaning properties are good;if it is 10 μm or less, an image with high image quality at highresolution can be obtained.

In addition, the ratio of the volume average particle diameter (Dv) tothe number average particle diameter (Dn) Dv/Dn in a resin particle (A)is preferably from 1.0 to 2.0, more preferably from 1.0 to 1.9. WhenDv/Dn is from 1.0 to 2.0, the powder properties such as the powderflowability, the electrostatic property, and the dustability do not havethe possibility of being inhomogeneous. When the resin particle is usedas a toner, Dv/Dn is preferably from 1.0 to 1.5, more preferably from1.0 to 1.4. If Dv/Dn is from 1.0 to 1.5, the resolution is good.

In the present invention, the extent of unevenness of the surface of aresin particle (A) can be evaluated on the basis of the shape factor(SF-2), and the ratio of the center line average surface roughness tothe volume average particle diameter.

The shape factor (SF-2) of a resin particle (A) is from 110 to 300. Theupper limit is preferably 250, more preferably 230, particularlypreferably 200; the lower limit is more preferably 115, particularlypreferably 120, most preferably 125.

Additionally, the ratio of the center line surface average roughness tothe volume average particle diameter, of a resin particle (A), ispreferably from 0.001 to 0.1, more preferably from 0.002 to 0.08,particularly preferably from 0.002 to 0.06, most preferably from 0.003to 0.05.

When the values are within the above ranges, the useful effects asindicated below can be obtained depending on applications of the resinparticle. For instance, when the resin particles are used as a paintadditive or a coating additive, or a cosmetics additive, the maskingability is increased due to an increase in light scattering effect,thereby improving the brightness and opacity. Also, when the resinparticles are used as a cosmetics additive or paper coating additive,the oil absorbance and retention of oil components are improved. Whenthe particles are used as an abrasive, the coefficient of friction ofthe particles is increased, thereby improving abrasion property. Inaddition, when the particles are used as a material for slush molding, ahot melt adhesive, or a powder paint, the powder flowing properties andthe properties of sharp break of powder flow during coating tend to beimproved.

Moreover, when the values are within the ranges, where the resinparticles are employed as a toner, the blade cleaning properties of thetoner becomes good.

In the present invention, the shape factor (SF-2) of a resin particle(A) is a value that is obtained by the evaluation that involves randomlysampling 100 resin particle images amplified to a magnification of 500times by means of an electron microscope (e.g., including FE-SEM (S-800)manufactured by Hitachi Co., Ltd.; also the same hereinafter),introducing the image information into an image analyzer [e.g.,including nexus NEW CUBE ver. 2.5 (manufactured by NEXUS) and Luzex III(manufactured by Nicore); also the same hereinafter)] via an interfaceand analyzing, and then subjecting to the calculation by Equation (1):(SF-2)=100×(P)²/{4π×(Y)}  (1)where (P) represents the perimeter length of the resin particle and (Y)represents the projection area of the resin particle.

In the present invention, the center line average surface roughness of aresin particle (A) can be determined by means of a scanning probemicroscope system (AFM, including, for example, a product from ToyoTechnica Inc.). The volume average particle diameter (Dv) and the numberaverage particle diameter (Dn) of the resin particle (A) can bedetermined using a Coulter counter particle size measuring apparatus[e.g., trade name: Multisizer III (manufactured by Beckman Coulter) or alaser type particle size distribution measuring apparatus [e.g., tradename: LA-920 (manufactured by Horiba, Ltd.)].

The upper limit of the ratio of the volume average particle diameter ofthe primary particle of a filler (b*) as described later thatconstitutes at least a portion of a filler (b) and forms the outer shelllayer (S) to the volume average particle diameter of a resin particle(A) is normally preferably 0.1, more preferably 0.01, and particularlypreferably 0.005.

In addition, the volume average particle diameter of the primaryparticle of a filler (b*) forming the outer shell layer (S) can beselected that is within the above particle diameter range. For instance,with a resin particle (A) having a volume average particle diameter of 1μm, the volume average particle diameter of the primary particle ispreferably from 0.001 to 0.1 μm , more preferably from 0.001 to 0.005μm; for a resin particle (A) having a volume average particle diameterof 10 μm, the volume average particle diameter of the primary particleis preferably from 0.001 to 1 μm, more preferably from 0.001 to 0.1 μm,particularly preferably from 0.002 to 0.05 μm; for a resin particle (A)having a volume average particle diameter of 100 μm, the volume averageparticle diameter of the primary particle is preferably from 0.001 to 10μm, more preferably from 0.002 to 0.5 μm. The volume average particlediameter of the primary particle of an inorganic filler (b1) ispreferably as a whole from 0.001 to 3 μm, more preferably from 0.002 to0.5 μm. Additionally, with a resin particle for a toner, the volumeaverage particle diameter of the primary particle of a filler (b*) ispreferably from 0.001 to 0.5 μm, more preferably from 0.001 to 0.1 μm,particularly preferably from 0.002 to 0.05 μm.

The volume average particle diameter of a filler (b*) is preferablydetermined by means of a laser type particle size distribution measuringapparatus when the volume average particle diameter is 0.1 μm or more;when the volume average particle diameter is 0.1 μm or less, the volumeaverage particle diameter is preferably calculated from the BET specificsurface area and the true specific gravity. The BET specific surfacearea can usually be determined by an apparatus based on the nitrogenadsorption process [e.g., trade name: QUQNTASORB (manufactured byQUANTACHROME)]. Dividing the inverse number of the BET specific surfacearea of a filler (b*) by the true specific gravity of a filler (b*) canlead to the determination of the primary particle diameter of a filler(b*).

The filler (b) content in a resin particle (A) is preferably from 0.01to 50%, more preferably from 0.05 to 45%, particularly preferably from0.1 to 40%.

The (b*) content in a resin particle (A) is preferably from 0.01 to 20%,more preferably from 0.05 to 18%, particularly preferably from 0.1 to15%.

The proportion of (b*) in a filler (b) is preferably 10% or more, morepreferably 20% or more.

The filler (b*) preferably has the effect of increasing the viscosity ofthe outer shell layer (S) in the outer shell layer (S) forming step. Theviscosity when the filler (b*) alone is dispersed in a solvent (s) asdescribed later at a temperature of 25° C. in a filler volume fractionof 0.3 is preferably from 50 to 100,000 mPa·s, more preferably from 100to 50,000 mPa·s, particularly preferably from 150 to 30,000 mPa·s.

The larger the aspect ratio of a filler (b*), the higher the effect ofincreasing the viscosity of the outer shell layer (S), and the effect ishigh that forms unevenness on the resin particle (A) surface. Thus, asthe aspect ratio of a filler (b*) is increased, unevenness can be formedon the resin particle surface with a low amount of addition of a filler(b*). The aspect ratio is preferably from 1.5 to 1,000, more preferablyfrom 2 to 800, particularly preferably from 2.5 to 600, most preferablyfrom 3 to 500.

The filler (b), at least a portion of which forms the outer shell layer(S), thereby being the filler (b*), is not particularly limited as longas the filler (b) is an inorganic or organic particulate material thatdoes not dissolve in solvents (s) as described later, and may be usedalone or in combination with two or more species depending on thepurpose. More specifically, an inorganic filler (b1), an organic filler(b2), or a combination of an inorganic filler (b1) and an organic filler(b2) may be acceptable. When used as resin particles for toners, in anorganic filler (b2) are contained a colorant, wax, charge controllingagent, and the like that are generally used for resin particles fortoners. In addition, the fillers can also be made to be a filler (b*) byfiller surface treatment described below.

The inorganic fillers (b1) include, for example, metal oxides such assilica, diatom earth, alumina, zinc oxide, titania, zirconia, calciumoxide, magnesium oxide, iron oxide, copper oxide, tin oxide, chromiumoxide, antimony oxide, yttrium oxide, cerium oxide, samarium oxide,lanthanum oxide, tantalum oxide, terbium oxide, europium oxide,neodymium oxide, and ferrites; metal hydroxides such as calciumhydroxide, magnesium hydroxide, aluminum hydroxide, and basic magnesiumcarbonate; metal carbonate such as heavy calcium carbonate, lightcalcium carbonate, zinc carbonate, barium carbonate, dawsonite, andhydrolytic; metal sulfates such as calcium sulfate, barium sulfate, andplaster fiber; metal silicates such as calcium silicate (wallasnite,xonotlite), kaolin, clay, talc, mica, montmorillonite, bentonite,activated white earth, sepiolite, imogolite, serisite, glass fiber,glass beads, and glass flakes; metal nitrides such as aluminum nitride,boron nitride, and silicon nitride; metal titanates such as potassiumtitanate, calcium titanate, magnesium titanate, barium titanate, andlead zirconate titanate aluminum borate; metal borates such as zincborate, and aluminum borate; metal phosphates such as tricalciumphosphate; metal sulfates such as molybdenum sulfate; metal carbidessuch as silicon carbide; carbons such as carbon black, graphite, andcarbon fiber; and other fillers.

Of these, fillers (b*) that form the outer shell layer (S) preferablyinclude metal oxides, metal carbonates, and metal silicates, morepreferably include silica, alumina, zinc oxide, titania, calciumsilicate, kaolin, clay, talc, and mica, particularly preferably includesilica, alumina and titania.

The organic fillers (b2) include, for example, resin beads such as vinylresin, urethane resin, epoxy resin, ester resin, polyamides, polyimides,silicone resin, fluorine resin, phenol resin, melamine resin,benzoguanamine-based resin, urea resin, aniline resin, ionomer resin,polycarbonate, cellulose, mixtures thereof. Also, the organic fillers(b2) include organic waxes such as ester-based waxes (carnauba wax,montan wax, rice wax, etc), polyolefin-based waxes (polyethylene,polypropylene, etc), paraffin-based wax, ketone-based wax, ether-basedwax, long chain (C30 or more) aliphatic alcohols, long chain (C30 ormore) aliphatic acids and mixtures thereof. In addition, the colorantsthat are generally used such as a variety of organic dyes or organicpigments, e.g., azo, phthalocyanine, condensation polycyclic, andcoloring lake dyes or pigments, and derivatives thereof can be used.

Of these, preferable fillers (b*) that form the outer shell layer (S)include a variety of organic dyes or organic pigments such as azo,phthalocyanine, condensation polycyclic, and coloring lake dyes orpigments, and derivatives thereof.

In addition, with resin particles for toners, the fillers (b) that mayuse include colorants, waxes and charge-controlling agents that aregenerally used. The charge-controlling agents of the above inorganic ororganic fillers include, for example, nigrosin-based dyes,triphenylmethane-based dyes, chromium-containing metal complex dyes,molybdic acid chalate pigments, rhodamine-based dyes, alkoxy-basedamines, quarternary ammonium salts (including fluorine-modifiedquarternary ammonium salts), alkylamides, phosphorus elements orcompounds, tungsten elements or compounds, fluorine based surfactants,metal salicylates and metal salts of salicylic acid derivatives. Morespecifically, the charge-controlling agents include, for example,Bontoron 03 of nigrosin based dyes, Bontron P-51 of quarternary ammoniumsalts, Bontoron S-34 of metal-bearing azo dyes, E-82 of oxynaphthoicacid based metal complexes, E-84 of salicylic acid based metalcomplexes, E-89 of phenol based condensation products (the aboveproducts manufactured by Orient Chemical Industries, Ltd.), TP-302 andTP-415 of quarternary ammonium salt molybdenum complexes (manufacturedby Hodogaya Chemical Co., Ltd.), Copy charge PSY VP2038 of quarternaryammonium salts, Copy blue PR of triphenylmethane derivatives, Copycharge NEG VP2036 and Copy charge NX VP434 of quarternary ammonium salts(manufactured by Hoechst AG), LRA-901, LR-147 of boron complexes(manufactured by Japan Carlit Co., Ltd.), copper phthalocyanine,perylene, quinacridone, azo based dyes, polymer compounds havingfunctional groups such as a sulfo group, a carboxyl group, and aquarternary ammonium salts.

In order that the filler (b*) forms an outer shell layer proximate tothe surface of the resin particle (A), the property of the filler (b*)surface preferably has slight hydrophilicity although it is basicallyhydrophobic. If the filler (b) surface is free of hydrophilic groups andexhibits strong hydrophobicity, the filler (b) is dispersed within theinside of the resin particle (A). Moreover, if the filler (b) surfaceexhibits sufficiently strong hydrophilicity to the extent that thefiller (b)alone disperses in water, the filler (b) will be detached tothe aqueous medium (W) side when a dispersion liquid (D) as describedlater is dispersed in the aqueous medium (W).

Accordingly, for the deformation of the shape of the resin particle (A),the optimization of the hydrophilicity/hydrophobicity balance of thefiller (b) surface is required that involves forming the resin particle(A) by means of the method as indicated below for the filler (b) of somedifferent levels of the degree of hydrophilicity/hydrophobicity by thesurface treatment of the filler (b) as described later, and confirmingthe shape of the resin particle (A) and the outer shell layer (S).

The evaluation methods of the hydrophilicity and hydrophobicity of afiller (b) include a process that involves adding, to a water-insolublesolvent dispersion liquid of the filler (b) or a water-insoluble solventdiluted liquid of the dispersion liquid (D) as described later (bothdiluted by a factor of 10000), water the amount of which is equivalentto the above liquid and forcibly agitating the resulting liquid, andthen observing the separation speed of the oil and water phases and theoil water orientation of the filler (b). The water-insoluble solventsthat may be used include, for example, toluene, xylene, methyl ethylketone, ethyl acetate, and other solvents. If the total amount of thefiller (b) migrates to the water phase, making the filler (b)hydrophobic via surface treatment is required because the surfacehydrophilicity of the filler (b) is too high. In addition, if the totalamount of the filler (b) immediately (within one minute) migrates to theoil phase after forced agitation, hydrophilicity needs to be imparted bysurface treatment since the surface hydrophobicity of the filler (b) istoo strong. After the forced agitation, it is ideal that the separationbetween the oil and water mildly occurs, and the filler (b) behaves toorient adjacent to the interface of the oil and water, but the criteriaof the evaluation of the observation is only a target.

For the optimization of the surface hydrophilicity/hydrophobicitybalance of a filler (b), the filler (b) is preferably surface-treatedwith a surface treating agent (d) such as a silicone oil, a couplingagent (e.g., a silane coupling agent, a titanate coupling agent, analuminate coupling agent, or the like), an amine compound, or acommercially available various pigment dispersing agent.

Examples of the silicone oil include straight silicone oils such asdimethyl silicone oil, methyl phenyl silicone oil, and methyl hydrogensilicone oil, and modified silicone oils such as methacrylic acidmodified silicone oil, epoxy-modified silicone oil, fluorine-modifiedsilicone oil, polyether-modified silicone oil, and amino-modifiedsilicone oil. In addition, the silane coupling agents include, forexample, organoalkoxysilanes, organochlorosilanes, organosilazanes,organodisilazanes, organosiloxanes, organodisiloxanes, andorganosilanes, and the like.

The amine compounds that may be used include compounds that arecompatible with solvents(s) as described later and have one or more ofany of a primary amine group, a secondary amine group, and a tertiaryamine group, and in particular compounds having a tertiary amine groupbeing free of active hydrogen are preferably used because there is apossibility that the amine compounds react with a precursor (a0) of theresin (a).

The tertiary amine compounds include, for example, trimethylamine,N,N′-dimethylaminodiethyl ether, tetramethylhexamethylenediamine,tetramethylethylenediamine, dimethylethanolamine,N-methyl-N′-(2-dimethylamino)ethylpiperazine, 1,2-dimethylimidazole,triethylenediamine, N,N,N′,N″,N″-pentamethyldiethylenetriamine,N,N,N′,N″,N″-pentamethyldipropylenetriamine, tetramethylguanidine,1,8-diazabicyclo(5,4,0)undecene-7, bis(2-morphorinoethyl) ether, and thelike; two or more of these may be used in combination. Of these,particularly preferable species include trimethylamine,1,8-diazabicyclo(5,4,0)undecene-7, and bis(2-morphorinoethyl) ether.

The process of surface treating a filler (b) is not particularlylimited, but well-known methods are applicable; for example, thefollowing the methods [1] to [5] and the combinations thereof, and thelike can be applied.

[1] A process involving adding a surface treating agent (d) to a filler[b], and then dry-treating the resulting material by means of a Henschelmixer, a Lodige mixer, or the like.

[2] A process involving melting and kneading a resin (a) and a filler(b) by means of a kneader, as necessary, in the presence of a solvent(s) (integral blend process).

[3] A process involving dispersing and wet-treating, in a solvent (s), afiller (b) and a surface treating agent (d), as required, a resin (a) bymeans of a beads mill, or the like.

[4] A process involving dispersing a filler (b) in water, adding asurface treating agent (d) to the resulting liquid, wet-treating it, andsubsequently replacing the water with a solvent (s).

[5] A process involving directly adding a surface treating agent (d) toa dispersion liquid (D) containing a filler (b), and then dispersing theresulting material with a disperser such as a homomixer, Ebara milder,or the like.

The resin (a) in the present invention may be a thermoplastic resin or athermosetting resin, and examples of the resin (a) that may be usedinclude a vinyl resin, an urethane resin, an epoxy resin, an esterresin, a polyamide, a polyimide, a silicone resin, a phenol resin, amelamine resin, a urea resin, an aniline resin, an ionomer resin, apolycarbonate, and mixtures thereof. Of these, from the viewpoint ofhomogeneous fine spherical resin particles being readily obtainable, avinyl resin, an urethane resin, an epoxy resin, an ester resin, andmixtures thereof are preferable, a vinyl resin, an urethane resin, anester resin and mixtures thereof are more preferable, a vinyl resin anester resin and mixtures thereof particularly preferable.

Hereinbelow, these resins to be preferably used as the resin (a), thatis, vinyl resins, urethane resins, epoxy resins, and ester resins willbe described, but the other resins mentioned above can also be used asthe resin (a).

Vinyl resins are homopolymers or copolymers of vinyl monomers.

In polymerization, a well-known polymerization catalyst or the like canbe used.

As vinyl monomers, the following compounds (1) to (10) can be used.

(1) Vinyl hydrocarbons:

(1-1) Aliphatic vinyl hydrocarbons:

alkenes having 2 to 12 carbon atoms (e.g., ethylene, propylene, butene,isobutylene, pentene, heptene, diisobutylene, octene, dodecene,octadecene, and α-olefins having 3 to 24 carbon atoms); and alkadieneshaving 4 to 12 carbon atoms (e.g., butadiene, isoprene, 1,4-pentadiene,1,6-hexadiene, and 1,7-octadiene).

(1-2) Alicyclic vinyl hydrocarbons:

mono- or di-cycloalkenes having 6 to 15 carbon atoms (e.g., cyclohexene,vinylcyclohexene, and ethylidenebicycloheptene); mono- ordi-cycloalkadienes having 5 to 12 carbon atoms (e.g.,(di)cyclopentadiene); terpenes (e.g., pinene, limonene, and indene); andthe like.

(1-3) Aromatic vinyl hydrocarbons:

styrene; hydrocarbyl(alkyl, cycloalkyl, aralkyl, and/or alkenyl eachhaving 1 to 24 carbon atoms)-substituted styrene (e.g., α-methylstyrene,vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene,butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene,crotylbenzene, divinylbenzene, divinyltoluene, divinylxylene, andtrivinylbenzene); vinylnaphthalene; and the like.

(2) Carboxyl group-containing vinyl monomers and salts thereof:

unsaturated monocarboxylic acids having 3 to 30 carbon atoms (e.g.,(meth)acrylic acid, crotonic acid, isocrotonic acid and cinnamic acid);unsaturated dicarboxylic acids having 3 to 30 carbon atoms or anhydridesthereof (e.g., maleic acid (anhydride), fumaric acid, itaconic acid,citraconic acid (anhydride), and mesaconic acid); monoalkyl (having 1 to24 carbon atoms) esters of unsaturated dicarboxylic acids having 3 to 30carbon atoms (e.g., monomethyl ester of maleic acid, monooctadecyl esterof maleic acid, monoethyl ester of fumaric acid, monobutyl ester ofitaconic acid, glycol monoether of itaconic acid, and monoeicosyl esterof citraconic acid);and the like.

Examples of salts of the carboxyl group-containing vinyl monomersinclude alkali metal salts (e.g., sodium salts and potassium salts),alkaline-earth metal salts (e.g., calcium salts and magnesium salts),ammonium salts, amine salts, and quaternary ammonium salts. The aminesalts are not limited to any specific ones as long as they are aminecompounds, but primary amine salts (e.g., ethylamine salts, butylaminesalts, and octylamine salts), secondary amine salts (e.g., diethylaminesalts and dibutylamine salts), and tertiary amine salts (e.g.,triethylamine salts and tributylamine salts) can be mentioned, forexample. As the quaternary ammonium salts, tetraethylammonium salts,lauryltriethylammonium salts, tetrabutylammonium salts,lauryltributylammonium salts, and the like can be mentioned.

Specific examples of salts of the carboxyl group-containing vinylmonomers include sodium acrylate, sodium methacrylate, monosodiummaleate, disodium maleate, potassium acrylate, potassium methacrylate,monopotassium maleate, lithium acrylate, cesium acrylate, ammoniumacrylate, calcium acrylate, aluminum acrylate, and the like.

(3) Sulfo group-containing vinyl monomers and salts thereof:

alkenesulfonic acids having 2 to 14 carbon atoms (e.g., vinylsulfonicacid, (meth)allylsulfonic acid, and methylvinylsulfonic acid);styrenesulfonic acid and alkyl (having 2 to 24 carbon atoms) derivativesthereof (e.g., α-methylstyrenesulfonic acid); sulfo (hydroxy)alkyl-(meth)acrylates having 5 to 18 carbon atoms (e.g.,sulfopropyl(meth)acrylate, 2-hydroxy-3-(meth)acryloxypropylsulfonicacid, 2-(meth)acryloyloxyethanesulfonic acid, and3-(meth)acryloyloxy-2-hydroxypropanesulfoic acid);sulfo(hydroxy)alkyl(meth)acrylamides having 5 to 18 carbon atoms (e.g.,2-(meth)acryloylamino-2,2-dimethylethanesulfonic acid,2-(meth)acrylamide-2-methylpropanesulfonic acid, and3-(meth)acrylamide-2-hydroxypropanesulfonic acid); alkyl (having 3 to 18carbon atoms) allylsulfosuccinic acids (e.g., propylallylsulfosuccinicacid, butylallylsulfosuccinic acid, and 2-ethylhexyl-allylsulfosuccinicacid); poly(n=2 to 30)oxyalkylene(oxyethylene, oxypropylene,oxybutylene: homo, random, or block)mono(meth)acrylate sulfates (e.g.,poly(n=5 to 15)oxyethylene monomethacrylate sulfate and poly(n=5 to15)oxypropylene monomethacrylate sulfate); polyoxyethylene polycyclicphenyl ether sulfates (e.g., sulfates represented by the general formula(1-1) or (1-2)); sulfonic acids represented by the general formula(1-3)); salts thereof; and the like.

It is to benoted that counter ions mentioned with reference to “(2)carboxyl group-containing vinyl monomers and salts thereof” or the likeare used for the salts.

wherein R represents an alkyl group having 1 to 15 carbon atoms, AOrepresents an oxyalkylene group having 2 to 4 carbon atoms, and whereinwhen n is plural, oxyalkylene groups may be the same or different, andwhen different, they may be random, block and/or combination of randomand block, Ar represents a benzen ring, n is an integer of 1 to 50, andR′ represents an alkyl group having 1 to 15 carbon atoms which may besubstituted by a fluorine atom.

(4) Phosphono group-containing vinyl monomers and salts thereof:

(meth)acryloyloxyalkyl (having 1 to 24 carbon atoms) monophosphates(e.g., 2-hydroxyethyl(meth)acryloyl phosphate andphenyl-2-acryloyloxyethyl phosphate), and (meth)acryloyloxyalkyl (having1 to 24 carbon atoms)phosphonic acids (e.g.,2-acryloyloxyethylphosphonic acid).

(5) Hydroxyl group-containing vinyl monomers:

hydroxystyrene, N-methylol(meth)acrylamide, hydroxyethyl(meth)acrylate,hydroxypropyl(meth)acrylate, polyethylene glycol mono(meth)acrylate,(meth)allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-butene-3-ol,2-butene-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, and allyl ether of sucrose, and the like.

(6) Nitrogen-containing vinyl monomers:

(6-1) Amino group-containing vinyl monomers:

aminoethyl(meth)acrylate, dimethylaminoethyl(meth)acrylate,diethylaminoethyl(meth)acrylate, t-butylaminoethyl methacrylate,N-aminoethyl(meth)acrylamide, (meth)allylamine,morpholinoethyl(meth)acrylate, 4-vinylpyridine, 2-vinylpyridine,crotylamine, N,N-dimethylaminostyrene, methyl α-acetaminoacrylate,vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone,N-arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole,aminopyrrole, aminoimidazole, aminomercaptothiazole, salts thereof, andthe like.

(6-2) Amide group-containing vinyl monomers:

(meth)acrylamide, N-methyl(meth)acrylamide, N-butylacrylamide,diacetoneacrylamide, N-methylol(meth)acrylamide,N,N′-methylene-bis(meth)acrylamide, cinnamamide, N,N-dimethylacrylamide,N,N-dibenzylacrylamide, methacryl formamide, N-methyl-N-vinylacetamide,and N-vinylpyrrolidone, and the like.

(6-3) Nitrile group-containing vinyl monomers having 3 to 10 carbonatoms:

(meth)acrylonitrile, cyanostyrene, cyanoacrylate, and the like.

(6-4) Quaternary ammonium cation group-containing vinyl monomers:

quaternization products (obtained using a quaternizing agent such asmethyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonateor the like) of tertiary amine group-containing vinyl monomers such asdimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate,dimethylaminoethyl(meth)acrylamide, diethylaminoethyl(meth)acrylamide,diallylamine, and the like (e.g., dimethyldiallylammonium chloride andtrimethylallylammonium chloride).

(6-5) Nitro group-containing vinyl monomers having 8 to 12 carbon atoms:

nitrostyrene and the like.

(7) Epoxy group-containing vinyl monomers having 6 to 18 carbon atoms:

glycidyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, p-vinylphenyloxide, and the like.

(8) Halogen-containing vinyl monomers having 2 to 16 carbon atoms:

vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride,chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene,tetrafluorostyrene, chloroprene, and the like.

(9) Vinyl esters, vinyl (thio)ethers, vinyl ketones, and vinyl sulfones:

(9-1) vinyl esters having 4 to 16 carbon atoms:

vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallylphthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate,methyl 4-vinylbenzoate, cyclohexyl methacrylate, benzyl methacrylate,phenyl (meth)acrylate, vinyl methoxyacetate, vinyl benzoate, ethylα-ethoxyacrylate, alkyl(meth)acrylates having an alkyl group containing1 to 50 carbon atoms (e.g., methyl(meth)acrylate, ethyl(meth)acrylate,propyl(meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl(meth)acrylate,dodecyl (meth)acrylate, hexadecyl(meth)acrylate, heptadecyl(meth)acrylate, and eicosyl(meth)acrylate), dialkyl fumarates (whose twoalkyl groups are straight, branched or alicyclic groups having 2 to 8carbon atoms), dialkyl maleates (whose two alkyl groups are straight,branched or alicyclic groups having 2 to 8 carbon atoms),poly(meth)allyloxyalkanes (e.g., diallyloxyethane, triallyloxyethane,tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, andtetramethallyloxyethane), vinyl-based monomers having apolyalkyleneglycol chain [e.g., polyethylene glycol (molecular weight:300) mono(meth)acrylate, polypropylene glycol (molecular weight: 500)monoacrylate, methyl alcohol-ethylene oxide (hereinafter referred to asEO) (10 mol) adduct (meth)acrylate, and lauryl alcohol-EO (30 mol)adduct (meth)acrylate], and poly(meth)acrylates (e.g.,poly(meth)acrylates of polyhydric alcohols: ethylene glycoldi(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycoldi(meth)acrylate, trimethylolpropane tri(meth)acrylate, and polyethyleneglycol di(meth)acrylate), and the like.

(9-2) Vinyl (thio)ethers having 3 to 16 carbon atoms:

vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butylether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl2-methoxyethyl ether, methoxybutadiene, vinyl 2-butoxyethyl ether,3,4-dihydro-1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, vinyl2-ethylmercaptoethyl ether, acetoxystyrene, and phenoxystyrene, and thelike.

(9-3) Vinyl ketones having 4 to 12 carbon atoms (e.g., vinyl methylketone, vinyl ethyl ketone, and vinyl phenyl ketone):

vinyl sulfones having 2 to 16 carbon atoms (e.g., divinyl sulfide,p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone,divinyl sulfone, and divinyl sulfoxide), and the like.

(10) Other vinyl monomers:

isocyanatoethyl (meth)acrylate, m-isopropenyl-α, α-dimethylbenzylisocyanate, and the like.

Among these vinyl monomers, vinyl hydrocarbons, carbbxylgroup-containing vinyl monomers and salts thereof, sulfonic acidgroup-containing vinyl monomers and salts thereof, hydroxylgroup-containing vinyl monomers, and nitrogen-containing vinyl monomersare preferably used, more preferably, vinyl hydrocarbons, carboxylgroup-containing vinyl monomers and salts thereof, and sulfonic acidgroup-containing vinyl monomers and salts thereof, even more preferablyaromatic vinyl-based hydrocarbons, carboxyl group-containing vinylmonomers and salts thereof, and sulfonic acid group-containing vinylmonomers and salts thereof.

Among vinyl resins, as polymers obtained by copolymerizing vinylmonomers(copolymers of vinyl monomers), polymers obtained by copolymerizing twoor more of the monomers mentioned in (1) to (10) in any ratio are used.Examples of such copolymers include styrene-(meth)acrylate copolymer,styrene-butadiene copolymer, (meth)acrylic acid-(meth)acrylatecopolymer, styrene-acrylonitrile copolymer, styrene-maleic acid(anhydride) copolymer, styrene-(meth)acrylic acid copolymer,styrene-(meth)acrylic acid-divinylbenzene copolymer, andstyrene-styrenesulfonic acid-(meth)acrylate copolymer, and the like.

As ester resins, polycondensation products of polyols withpolycarboxylic acids, acid anhydrides thereof or lower alkyl estersthereof (alkyl groups having 1 to 4 carbon atoms), and the like can beused.

In polycondensation reaction, a well-known polycondensation catalyst orthe like can be used.

As polyols, diols (11) and polyols (12) having 3 to 6 or more hydroxylgroups can be used.

As polycarboxylic acids, acid anhydrides thereof, and lower alkyl estersthereof, dicarboxylic acids (13), polycarboxylic acids (14) having 3 to6 or more carboxyl groups, acid anhydrides thereof, and lower alkylesters thereof can be used.

Examples of the diols (11) include alkylene glycols having 4 to 30carbon atoms (e.g., ethylene glycol, 1,2-propylene glycol, 1,3-propyleneglycol, 1,4-butanediol, 1,6-hexanediol, octanediol, decanediol,dodecanediol, tetradecanediol, neopentyl glycol, and2,2-diethyl-1,3-propanediol), alkylene ether glycols having a molecularweight of 50 to 10,000 (e.g., diethylene glycol, triethylene glycol,dipropylene glycol, polyethylene glycol, polypropylene glycol, andpolytetramethylene ether glycol), alicyclic diols having 6 to 24 carbonatoms (e.g., 1,4-cyclohexane dimethanol and hydrogenatedbisphenol A),alkylene oxides (hereinafter, simply referred to as “AO”) [e.g., EO,propylene oxide (hereinafter referred to as PO), and butylene oxide(hereinafter referred to as BO)] (2 to 100 mol) adducts of theabove-mentioned alicyclic diols having a molecular weight of 100 to10,000 (e.g., EO (10 mol) adduct of 1,4-cyclohexane dimethanol),

AO (EO, PO, BO and the like) (2 to 100 mol) adducts of bisphenols having15 to 30 carbon atoms (bisphenol A, bisphenol F, bisphenol S, and thelike), or polyphenols having 12 to 24 carbon atoms (e.g., catechol,hydroquinone, and resorcin, and the like) (e.g., bisphenol A•EO2-moladduct, bisphenol A•EO4-mol adduct, bisphenol A•PO 2-mol adduct,bisphenol A•PO 3-mol adduct, bisphenol A•PO 4-mol adduct, and the like);polylactonediols having weight average molecular weights (Mw) of from100 to 5,000 (e.g., poly-ε-caprolactonediol, and the like);polybutadienediols having Mw of from 1,000 to 20,000; and the like.

Of these, AO adducts of alkylene glycols and bisphenols are preferable,AO adducts of bisphenols and mixtures of AO adducts of bisphenols andalkylene glycols are more preferable.

Polyols (12) having 3 to 6 or more hydroxyl groups include, for example,aliphatic polyhydric alcohols having 3 to 6 or more hydroxyl groups andfrom 3 to 8 carbon atoms (e.g., glycerin, trimethylolethane,trimethylolpropane, pentaerythritol, sorbitan and sorbitol and thelike); alkylene (2 to 4 carbon atoms) oxide (2 to 100 mol) adducts oftrisphenols having 25 to 50 carbon atoms (e.g., trisphenol PA, and thelike) (e.g., trisphenol PA•EO 2-mol adduct, trisphenol PA•EO 4-moladduct, trisphenol PA•PO 2-mol adduct, trisphenol PA•PO 3-mol adduct,trisphenol PA•PO 4-mol adduct, and the like); alkylene (2 to 4 carbonatoms) oxide (2 to 100 mol) adducts of novolac resins havingpolymerization degrees of 3 to 50 (e.g., phenol novolac, cresol novolac,and the like) (e.g., phenol novolac PO 2-mol adduct, phenol novolac EO4-mol adducts, and the like); alkylene (2 to 4 carbon atoms) oxide (2 to100 mol) adducts of polyphenols having 6 to 30 carbon atoms (e.g.,pyrogallol, fluoroglucinol, 1,2,4-benzenetriol, and the like) (e.g.,pyrogallol EO 4-mol adduct, and the like); and acryl polyols havingpolymerization degrees of 20 to 2,000 [copolymers withhydroxyethyl(meth)acrylate and other vinyl monomers (e.g., styrene,(meth)acrylic acid, (meth)acrylic acid ester, or the like)]; and thelike.

Of these, AO adducts of aliphatic polyhydric alchols and novolac resinsare preferable, AO adducts of novolac resins are more preferable.

Examples of the dicarboxylic acids (13) include alkanedicarboxylic acidshaving 4 to 32 carbon atoms (e.g., succinic acid, adipic acid, sebacicacid, dodecenylsuccinic acid, azelaic acid, dodecanedicarboxylic acid,and octadecanedicarboxylic acid), alkenedicarboxylic acids having 4 to32 carbon atoms (e.g., maleic acid, fumaric acid, citraconic acid, andmesaconic acid), branched-chain alkenedicarboxylic acids having 8 to 40carbon atoms (e.g., dimer acid and alkenylsuccinic acids such asdodecenylsuccinic acid, pentadecenylsuccinic acid, andoctadecenylsuccinic acid), branched-chain alkanedicarboxylic acidshaving 12 to 40 carbon atoms (e.g., alkylsuccinic acids such asdecylsuccinic acid, dodecylsuccinic acid, and octadecylsuccinic acid),and aromatic dicarboxylic acids having 8 to 20 carbon atoms (e.g.,phthalic acid, isophthalic acid, terephthalic acid, andnaphthalenedicarboxylic acid), and the like.

Among these dicarboxylic acids (13), alkenedicarboxylic acids andaromatic dicarboxylic acids are preferably used, more preferablyaromatic dicarboxylic acids.

Examples of the polycarboxylic acids (14) having 3 to 4 or more carboxylgroups include aromatic polycarboxylic acids having 9 to 20 carbonatoms, such as trimellitic acid, and pyromellitic acid, and the like.

Examples of acid anhydrides of the dicarboxylic acids (13) and thepolycarboxylic acids (14) having 3 to 4 or more carboxyl groups includetrimellitic anhydride and pyromellitic anhydride. Examples of loweralkyl esters thereof include methyl esters, ethyl esters, and isopropylesters.

As ester resins, the diols, the polyols having 3 to 6 or more hydroxylgroups, the dicarboxylic acids, the polycarboxylic acids having 3 to 4or more carboxyl groups, and mixtures of two or more of them can be usedin any ratio. The equivalent ratio of hydroxyl group [OH] to carboxylgroup [COOH], that is, [OH]/[COOH] is preferably in the range of 2/1 to1/1, more preferably in the range of 1.5/1 to 1/1, even more preferablyin the range of 1.3/1 to 1.02/1.

Further, the ester equivalent (that is, a molecular weight per oneequivalent of ester group) in the ester resins is preferably in therange of 50 to 2,000, more preferably in the range of 60 to 1,000, evenmore preferably in the range of 70 to 500.

As urethane resins, polyaddition products of polyisocyanates (15) andactive hydrogen-containing compounds (a021) (e.g., water, the diols(11), the polyols (12) having 3 to 6 or more hydroxyl groups, thedicarboxylic acids (13), the polycarboxylic acids (14) having 3 to 4 ormore carboxyl groups, polyamines (16), and polythiols (17)), and thelike can be used.

In polyaddition reaction, a well-known polyaddition reaction catalyst orthe like can be used.

Examples of the polyisocyanates (15) include aromatic polyisocyanateshaving 6 to 20 carbon atoms (exclusive of the carbon in an NCO group;the same applies to the following description), aliphaticpolyisocyanates having 2 to 18 carbon atoms, alicyclic polyisocyanateshaving 4 to 15 carbon atoms, araliphatic polyisocynates having 8 to 15carbon atoms, and modification products of these polyisocyanates (e.g.,modified polyisocyanates having urethane, carbodiimide, allophanate,urea, biuret, urethodione, urethoimine, isocyanurate, or oxazolidonegroups), mixtures of two or more of them, and the like.

Examples of the aromatic polyisocyanates include 1,3- or 1,4-phenylenediisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4′-or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI [phosgenide ofcrude diaminophenylmethane [a condensation product of formaldehyde witharomatic amine (aniline) or a mixture containing such aromatic amine; amixture of diaminodiphenylmethane and a small amount (e.g., 5 to 20%) ofpolyamine having 3 or more amino groups]: polyallyl polyisocyanate(PAPI)], 1,5-naphthylene diisocyante, 4,4′,4″-triphenylmethanetriisocyanate, m- or p-isocyanatophenylsulfonyl isocyanate, mixtures oftwo or more of them, and the like.

Examples of the aliphatic polyisocyanates include ethylene diisocyanate,tetramethylene diisocyanate, hexamethylene diisocyanate (HDI),dodecamethylenediisocyanate, 1,6,11-undecane triisocyanate,2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate,2,6-diisocyanatomethyl caproate, bis(2-isocyanatoethyl) fumarate,bis(2-isocyanatoethyl) carbonate,2-isocyanatoethyl-2,6-diisocyanatohexanoate, mixtures of two or more ofthem, and the like.

Examples of the alicyclic polyisocyanates include isophoronediisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenatedMDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate(hydrogenated TDI),bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, 2,5- or2,6-norbornane diisocyanate, mixtures of two or more of them, and thelike.

Examples of the araliphatic polyisocyanates include m- or p-xylylenediisocyanate (XDI), α, α, α′, α′-tetramethylxylylene diisocyanate(TMXDI), mixtures of two or more of them, and the like.

Examples of the modification products of polyisocyanates includemodified polyisocyanates having urethane, carbodiimide, allophanate,urea, biuret, urethodione, urethoimine, isocyanurate and/or oxazolidonegroups, such as modified MDI (e.g., urethane-modified MDI,carbodiimide-modified MDI, and trihydrocarbylphosphate-modified MDI),urethane-modified TDI, mixtures of two or more of them [e.g., a mixtureof the modified MDI and the urethane-modified TDI (isocyanate-containingprepolymer)], and the like.

Among these polyisocyanates, aromatic polyisocyanates, aliphaticpolyisocyanates, and alicyclic polyisocyanates are preferably used, morepreferably TDI, MDI, HDI, hydrogenated MDI, and IPDI.

As polyamines (16), aliphatic polyamines having 2 to 18 carbon atoms,aromatic polyamines having 6 to 20 carbon atoms, and the like can beused.

As aliphatic polyamines having 2 to 18 carbon atoms, (1) aliphaticpolyamines, (2) alkyl (having 1 to 4 carbon atoms)—or hydroxyalkyl(having 2 to 4 carbon atoms)—substituted aliphatic polyamines mentionedabove, (3) alicyclic or heterocycle-containing aliphatic polyamines, (4)aromatic ring-containing aliphatic amines having 8 to 15 carbon atoms,and the like can be used.

(1) Examples of the aliphatic polyamines include alkylenediamines having2 to 12 carbon atoms (e.g., ethylenediamine, propylenediamine,trimethylenediamine, tetramethylenediamine, and hexamethylenediamine),polyalkylene (having 2 to 6 carbon atoms) polyamines [e.g.,diethylenetriamine, iminobispropylamine, bis(hexamethylene)triamine,triethylenetetramine, tetraethylenepentamine, andpentaethylenehexamine], and the like.

(2) Examples of the alkyl (having 1 to 4 carbon atoms)—or hydroxyalkyl(having 2 to 4 carbon atoms)—substituted aliphatic polyamines mentionedabove include dialkyl (having 1 to 3 carbon atoms) aminopropylamine,trimethylhexamethylenediamine, aminoethylethanolamine,2,5-dimethyl-2,5-hexamethylenediamine, and methyliminobispropylamine,and the like.

(3) Examples of the alicyclic or heterocycle-containing aliphaticpolyamines include alicyclic polyamines having 4 to 15 carbon atoms{e.g., 1,3-diaminocyclohexane, isophoronediamine, menthenediamine,4,4′-methylenedicyclohexanediamine (hydrogenated methylenedianiline),and 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane}, andheterocyclic polyamines having 4 to 15 carbon atoms [e.g., piperazine,N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, and1,4-bis(2-amino-2-methylpropyl)piperazine], and the like.

(4) Examples of the aromatic ring-containing aliphatic amines (having 8to 15 carbon atoms) include xylylenediamine,tetrachloro-p-xylylenediamine, and the like.

As the above-mentioned aromatic polyamines having 6 to 20 carbon atoms,(1) unsubstituted aromatic polyamines, (2) aromatic polyamines nuclearlysubstituted by one or more alkyl groups (having 1 to 4 carbon atoms,such as methyl, ethyl, n- or i-propyl and butyl), (3) aromaticpolyamines having one or more electron-attracting groups such as halogen(e.g., Cl, Br, I, and F), alkoxy groups (e.g., methoxy and ethoxy), anda nitro group, and (4) secondary amino group-containing aromaticpolyamines, and the like can be used.

(1) Examples of the unsubstituted aromatic polyamines include 1,2-, 1,3-or 1,4-phenylenediamine, 2,4′- or 4,4′-diphenylmethanediamine, crudediphenylmethanediamine (polyphenylpolymethylenepolyamine),diaminodiphenyl sulfone, benzidine, thiodianiline,bis(3,4-diaminophenyl)sulfone, 2,6-diaminopyridine, m-aminobenzylamine,triphenylmethane-4,4′,4″-triamine, naphthylenediamine, mixtures of twoor more of them, and the like.

(2) Examples of the aromatic polyamines nuclearly substituted by one ormore alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, n-or i-propyl and butyl include 2,4- or 2,6-tolylenediamine, crudetolylenediamine, diethyltolylenediamine,4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-bis(o-toluidine),dianisidine, diaminoditolyl sulfone, 1,3-dimethyl-2,4-diaminobenzene,1,3-diethyl-2,4-diaminobenzene, 1,3-dimetnyl-2,6-diaminobenzene,1,4-diethyl-2,5-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene,1,4-dibutyl-2,5-diaminobenzene, 2,4-diaminomesitylene,1,3,5-triethyl-2,4-diaminobenzene,1,3,5-triisopropyl-2,4-diaminobenzene,1-methyl-3,5-diethyl-2,4-diaminobenzene,1-methyl-3,5-diethyl-2,6-diaminobenzene,2,3-dimethyl-1,4-diaminonaphthalene,2,6-dimethyl-1,5-diaminonaphthalene,2,6-diisopropyl-1,5-diaminonaphthalene,2,6-dibutyl-1,5-diaminonaphthalene, 3,3′,5,5′-tetramethylbenzidine,3,3′,5,5′-tetraisopropylbenzidine,3,3′,5,5′-tetramethyl-4,4′-diaminodiphenylmethane,3,3′,5,5′-tetraethyl-4,4′-diaminodiphenylmethane,3,3′,5,5′-tetraisopropyl-4,4′-diaminodiphenylmethane,3,3′,5,5′-tetrabutyl-4,4′-diaminodiphenylmethane,3,5-diethyl-3′-methyl-2′,4-diaminodiphenylmethane,3,5-diisopropyl-3′-methyl-2′,4-diaminodiphenylmethane,3,3′-diethyl-2,2′-diaminodiphenylmethane,4,4′-diamino-3,3′-dimethyldiphenylmethane,3,3′,5,5′-tetraethyl-4,4′-diaminobenzophenone,3,3′,5,5′-tetraisopropyl-4,4′-diaminobenzophenone,3,3′,5,5′-tetraethyl-4,4′-diaminodiphenyl ether,3,3′,5,5′-tetraisopropyl-4,4′-diaminodiphenyl sulfone, mixtures of twoor more of them, and the like.

(3) Examples of the aromatic polyamines having one or moreelectron-attracting groups such as halogen (e.g., a chlorine atom, abromine atom, an iodine atom, and a fluorine atom), alkoxy groups (e.g.,methoxy and ethoxy), and a nitro group as nuclear substituents includemethylenebis-o-chloroaniline, 4-chloro-o-phenylenediamine,2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline,4-bromo-1,3-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine,5-nitro-1,3-phenylenediamine, 3-dimethoxy-4-aminoaniline,4,4′-diamino-3,3′-dimethyl-5,5′-dibromo-diphenylmethane,3,3′-dichlorobenzidine, 3,3′-dimethoxybenzidine,bis(4-amino-3-chlorophenyl)oxide, bis(4-amino-2-chlorophenyl)propane,bis(4-amino-2-chlorophenyl)sulfone, bis(4-amino-3-methoxyphenyl)decane,bis(4-aminophenyl)sulfide, bis(4-aminophenyl)telluride,bis(4-aminophenyl)selenide, bis(4-amino-3-methoxyphenyl)disulfide,4,4′-methylenebis(2-iodoaniline), 4,4′-methylenebis(2-bromoaniline),4,4′-methylenebis(2-fluoroaniline), 4-aminophenyl-2-chloroaniline, andthe like.

(4) Examples of the secondary amino group-containing aromatic polyaminesinclude aromatic polyamines obtained by replacing some or all of —NH₂groups in the aromatic polyamines (1) to (3) with —NH—R′ groups (whereinR′ represents an alkyl group such as a lower alkyl group having 1 to 4carbon atoms e.g., methyl, ethyl, or the like), such as4,4′-di(methylamino)diphenylmethane, and1-methyl-2-methylamino-4-aminobenzene, and the like; polyamidepolyamines such as low molecular-weight polyamide polyamines obtained bycondensation of dicarboxylic acids (e.g., dimer acid) with excess (thatis, 2 or more mols per mol of the acid) polyamines (e.g., thealkylenediamines and the polyalkylenepolyamines mentioned above);polyether polyamines such as hydrides of cyanoethylation products ofpolyether polyols (e.g., polyalkylene glycol); and the like.

As polythiols (17), dithiols having 2 to 24 carbon atoms, tri- to hexa-or higher valent polythiols having 5 to 30 carbon atoms, and the likecan be used.

Examples of dithiols include ethylenedithiol, 1,4-butanedithiol,1,6-hexanedithiol, and the like.

Examples of polythiols include Capcure-3800 (manufactured by Japan EpoxyResins Co., Ltd.), polyvinylthiol, and the like.

Among these active hydrogen-containing compounds (a021), water, thediols (11), the polyols (12), the dicarboxylic acids (13), and thepolyamines (16) are preferably used, more preferably water, the diols(11), the polyols (12), and the polyamines (16), even more preferablythe diols (11), the polyols (12), and the polyamines (16).

As epoxy resins, ring-opening polymerization products of polyepoxides(18), polyaddition products of the polyepoxides (18) and the activehydrogen-containing compounds (a021), and curing reaction products ofthe polyepoxides (18) and acid anhydrides of the dicarboxylic acids (13)or the polycarboxylic acids (14) having 3 to 4 or more carboxyl groups,and the like can be used.

In ring-opening polymerization reaction, polyaddition reaction, andcuring reaction, a well-known catalyst or the like can be used.

The polyepoxide (18) is not limited to any specific one as long as ithas two or more epoxy groups in the molecule, but from the viewpoint ofmechanical characteristics of the cured product, it preferably has 2 to6 epoxy groups in the molecule.

The epoxy equivalent (that is, molecular weight per epoxy group) of thepolyepoxide (18) is preferably in the range of 65 to 1,000. The upperlimit is more preferably 500, even more preferably 300. The lower limitis more preferably 70, even more preferably 90. If the epoxy equivalentexceeds the above upper limit, the cross-linked structure tends to beloose, thus resulting in lowering of physical properties of the curedproduct, such as water resistance, chemical resistance, mechanicalstrength, and the like. On the other hand, it is difficult to get (orsynthesize) polyepoxides having an epoxy equivalent less than the abovelower limit.

As polyepoxides (18), aromatic polyepoxides, heterocycle-containingpolyepoxides, alicyclic polyepoxides, aliphatic polyepoxides, and thelike can be used.

As aromatic polyepoxides, glycidyl ethers of polyhydric phenols,glycidyl esters of polyhydric phenols, glycidyl aromatic polyamines, andglycidylation products of aminophenols, and the like can be used.

Examples of the glycidyl ethers of polyhydric phenols include bisphenolF diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidylether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether,bisphenol A diglycidyl halides, tetrachlorobisphenol A diglycidyl ether,catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinonediglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalenediglycidyl ether, dihydroxybiphenyl diglycidyl ether,octachloro-4,4′-dihydroxybiphenyl diglycidyl ether, tetramethylbiphenyldiglycidyl ether, dihydroxynaphthylcresol triglycidyl ether,tris(hydroxyphenyl)methane triglycidyl ether, dinaphthyltrioltriglycidyl ether, tetrakis(4-hydroxyphenyl)ethane tetraglycidyl ether,p-glycidylphenyldimethyltolyl bisphenol A glycidyl ether,trismethyl-tert-butyl-butylhydroxymethane triglycidyl ether,9,9′-bis(4-hydroxyphenyl)fluorene diglycidyl ether,4,4′-oxybis(1,4-phenylethyl)tetracresol glycidyl ether,4,4′-oxybis(1,4-phenylethyl)phenyl glycidyl ether,bis(dihydroxynaphthalene)tetraglycidyl ether, glycidyl ether of phenolor cresol novolac resin, glycidyl ether of limonene phenol novolacresin, diglycidyl ether obtained by the reaction between 2 mols ofbisphenol A and 3 mols of epichlorohydrin, polyglycidyl ethers ofpolyphenols obtained by condensation reaction of phenol with glyoxal,glutaraldehyde, or formaldehyde, polyglycidyl ether of polyphenolobtained by condensation reaction of resorcin with acetone, and thelike.

Examples of the glycidyl esters of polyhydric phenols include diglycidylphthalate, diglycidyl isophthalate, diglycidyl terephthalate, and thelike.

Examples of the glycidyl aromatic polyamines includeN,N-diglycidylaniline, N,N,N′,N′-tetraglycidylxylylenediamine, andN,N,N′,N′-tetraglycidyldiphenylmethanediamine, and the like.

Further, the epoxides include triglycidyl ether of p-aminophenol,diglycidyl urethane compounds obtained by the addition reaction oftolylene diisocyanate or diphenylmethane diisocyanate and glycidol, anddiglycidyl ethers of AO (EO or PO) (2 to 20 mol) adducts of bisphenol A(e.g., diglycidyl ether of EO (4 mol) adduct of bisphenol A).

As heterocyclic polyepoxides, trisglycidylmelamine can be used.

As alicyclic polyepoxides, vinylcyclohexene dioxide, limonene dioxide,dicyclopentadiene dioxide, bis(2,3-epoxycyclopentyl) ether, ethyleneglycol bisepoxydicyclopentyl ether,3,4-epoxy-6-methylcyclohexylmethyl-3′,4′-epoxy-6′-methylcyclohexanecarboxylate,bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate,bis(3,4-epoxy-6-methylcyclohexylmethyl)butylamine, dimer acid diglycidylester, and nuclear hydrogenation products of aromatic polyepoxides(e.g., hydrogenated bisphenol F diglycidyl ether and hydrogenatedbisphenol A diglycidyl ether) can be used, for example.

As aliphatic polyepoxides, polyglycidyl ethers of polyhydric aliphaticalcohols, polyglycidyl esters of polyvalent fatty acids, glycidylaliphatic amines, and the like can be used.

Examples of the polyglycidyl ethers of polyhydric aliphatic alcoholsinclude ethylene glycol diglycidyl ether, propylene glycol diglycidylether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidylether, polyethylene glycol diglycidyl ether, polypropylene glycoldiglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerolpolyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitolpolyglycidyl ether, polyglycerol polyglycidyl ether, and the like.

Examples of the polyglycidyl esters of polyvalent fatty acids includediglycidyl oxalate, diglycidyl maleate, diglycidyl succinate, diglycidylglutarate, diglycidyl adipate, diglycidyl pimelate, and the like.

Examples of the glycidyl aliphatic amines includeN,N,N′,N′-tetraglycidyl hexamethylenediamine, andN,N,N′,N′-tetraglycidyl ethylenediamine, and the like.

The aliphatic polyepoxides include (co)polymers of diglycidyl ethers andglycidyl(meth)acrylates.

Among these polyepoxides, aliphatic polyepoxy compounds and aromaticpolyepoxy compounds are preferably used. In the present invention, thepolyepoxides may be used in combination of two or more of them.

A resin (a) is a resin that constitutes a resin particle (A), and thenumber average molecular weight (Mn), the peak molecular weight, theglass transition point (Tg), the melting point, the SP value, thehydroxyl value, and the acid value of the resin (a) are preferably inthe following ranges.

For instance, when the resin particle (A) is used as a slush moldingresin or a powder paint, the Mn of the resin (a) is preferably from2,000 to 500,000, more preferably from 2,500 to 200,000, particularlypreferably 4,000 to 100,000.

In addition, when a resin (a) has a melting point, the melting point ofa resin (a) is preferably from 0 to 250° C., more preferably from 35 to200° C., particularly preferably from 40 to 180° C.

When a resin (a) is used as a toner resin particle, the number averagemolecular weight (Mn) of a resin (a) is preferably from 1,000 to 20,000,more preferably from 1,500 to 17,500, particularly preferably from 1,750to 15,000, most preferably from 2,000 to 12,500, from the viewpoints ofthermal storage stability, low-temperature fixing properties andanti-hot offset properties. Additionally, the peak molecular weight ispreferably from 1,000 to 30,000, more preferably from 1,500 to 10,000,particularly preferably from 2,000 to 8,000. If the peak molecularweight is 1,000 or more, the thermal storage stability is enhanced; whenit is 10,000 or less, the low-temperature fixing properties are better.

Moreover, the Mn and Mw of a resin (a) described above and below aredetermined by gel permeation chromatography (GPC; THF solvent, referencesubstance; polystyrene) Furthermore, the melting point is determined viaDSC (rate of temperature increase; 20° C./min).

In addition, the Tg of a resin (a) is preferably from −60 to 100° C.,more preferably from −40 to 80° C., particularly preferably from −30 to70° C. In particular, when a resin (a) is used as a toner resinparticle, the Tg of a resin (a) is preferably from 30 to 80° C., morepreferably from 35 to 75° C., particularly preferably from 40 to 70° C.,from the viewpoints of thermal storage stability and low-temperaturefixing properties.

Additionally, the Tg described above and below is evaluated from DSC(differential scanning calorimetry, the rate of temperature increase 20°C./min).

Moreover, the SP value of a resin (a) is preferably from 7 to 18, morepreferably from 8 to 16, particularly preferably from 9 to 14.

Furthermore, the SP value described above and below is calculated fromthe methods as described in “Polymer Engineering and Science, February,1974, Vol. 14, No. 2, pp. 147 to 154.

When a resin (a) is used as a toner resin particle, the hydroxyl valueof the resin (a) is preferably 5 or more, more preferably from 10 to120, particularly preferably from 20 to 80. The hydroxyl value of 5 ormore provides advantages in compatibility between thermal storagestability and low-temperature fixing properties. In addition, the acidvalue of the resin (a) is preferably from 1 to 30, more preferably from5 to 20. Giving an acid value to the resin (a) tends to allow the resin(a) to be of negative electricity. Moreover, the resin (a) having anacid value and a hydroxyl value, respectively, equal to upper limitvalues of these ranges or less, is hardly affected by circumstances ofhigh temperature, high humidity, low temperature and low humidity,thereby not suffering the deterioration of images.

The resin particle (A) may also contain therein, in addition to theresin (a) and the filler (b), additives (t) (e.g., a variety ofadditives such as a plasticizer, a filler, a mold release agent, acharge controlling agent, an ultraviolet absorbing agent, anantioxidant, an antistatic agent, a flame retardant, an antimicrobialagent, and an antiseptic agent).

The total content of additives (t) can be appropriately added dependingon various applications, but for example is preferably from 0.01 to200%, more preferably from 0.2 to 150%, particularly preferably from 0.1to 100%, based on the mass of the total of the resin (a) and filler (b).

Examples of a plasticizer (k) to be added include, but not limited to,the following (k1) to (k5) and mixtures of two or more of them:

(k1) phthalic acid esters having 8 to 60 carbon atoms (e.g., dibutylphthalate, dioctyl phthalate, butyl benzyl phthalate, and diisodecylphthalate);

(k2) aliphatic dibasic acid esters having 6 to 60 carbon atoms (e.g.,di-2-ethylhexyl adipate and 2-ethylhexyl sebacate);

(k3) trimellitic acid esters having 10 to 70 carbon atoms (e.g.,tri-2-ethylhexyl trimellitate and trioctyl trimellitate);

(k4) phosphoric acid esters having 6 to 60 carbon atoms (e.g., triethylphosphate, tri-2-ethylhexyl phosphate, and tricresyl phosphate); and

(k5) fatty acid esters having 8 to 50 carbon atoms (e.g., butyl oleate).

Among these plasticizers, (k1), (k2), (k3), and (k4) are preferablyused, more preferably (k1), (k2), and (k4), even more preferably (k1)and (k4).

A method for adding the additive (t) to the resin particles (A) is notlimited to any specific one. For example, in the preparing method ofresin particles according to the present invention (which will bedescribed later), the additive (t) may be added to an aqueous medium, ora mixture of the resin (a) and the additive (t) may be dispersed in anaqueous medium.

The processes of producing a resin particle (A) can include, forexample, a method that involves dispersing in an aqueous medium (W) afiller-containing dispersion liquid (D) obtained by dispersing a filler(b) in a dispersion liquid (D0) comprising a resin (a) and/or itsprecursor (a0) in solvent (s), forming a resin (a) by reaction when theprecursor (a0) is used, forming an oil-in-water dispersion liquid (D1),and removing the aqueous solvent from an aqueous dispersion containing aresin particle (A) obtained by solvent removal.

The process of producing an aqueous dispersion containing a resinparticle (A) is not particularly limited, and illustrative examplesthereof include a method that involves dispersing in an aqueous medium(W) a dispersion liquid (D) comprising a precursor (a0) of a resin (a),a filler (b) and a solvent (s) described later, and reacting theprecursor in the aqueous medium, a method that involves producing a deadpolymer of a resin (a), adding thereto a filler (b) and a solvent (s)described later, and dispersing the resulting material in an aqueousmedium (W), a method that involves reacting a precursor (a0) of a resin(a) in an aqueous medium(w) dispersed a dead polymer of the resin (a), afiller (b) and a solvent (s) described later, and the like.

The methods that involve dispersing in an aqueous medium (W) adispersion liquid (D) comprising a precursor (a0) of a resin (a), afiller (b) and a solvent (s) described later, and reacting the precursorin the aqueous medium, include, for example, the following the methods[1] and [2].

-   [1] A method of producing an aqueous dispersion of a resin    particle (A) by subjecting monomers as starting materials to    polymerization reaction such as suspension polymerization,    emulsification polymerization, seed polymerization or dispersion    polymerization, in the presence of a polymerization catalyst, a    filler (b) and a solvent (s) as described later in the case of a    vinyl resin.-   [2] A method of producing an aqueous dispersion of a resin    particle (A) that involves dispersing a precursor (a0) of a    resin (a) or a solvent solution of the precursor (a0) and a    filler (b) in an aqueous medium in the presence of an appropriate    dispersing agent in the case of polyaddition resins or condensed    resins such as an ester resin, an urethane resin and an epoxy resin,    then heating the resulting material or adding a curing agent (a    compound having at least two functional groups capable of reacting    with the precursor within the molecule) for curing.

The methods that involve producing a dead polymer of a resin (a) andthen dispersing the polymer in an aqueous medium include the methods [3]and [4] below.

-   [3] A method that involves dispersing a dispersion liquid comprising    a resin (a) prepared by polymerization reaction in advance (the    polymerization reaction processes may include any of addition    polymerization, ring-opening polymerization, polyaddition, addition    condensation, and condensation polymerization), a filler (b) and a    solvent (s) described later in an aqueous medium in the presence of    an appropriate dispersing agent, and then subjecting the resulting    liquid to heating, pressure reduction or the like to remove the    solvent.-   [4] A method that involves dissolving an appropriate emulsifier in a    dispersion liquid comprising a resin (a) prepared by polymerization    reaction in advance (the polymerization reaction processes may    include any of addition polymerization, ring-opening polymerization,    polyaddition, addition condensation, and condensation    polymerization), a filler (b) and a solvent (s) described later,    phase-inversion emulsifying the resulting liquid by water addition,    and then subjecting the resulting emulsion to heating, pressure    reduction or the like to remove the solvent.

Of the methods [1] to [4] above, the methods [1], [2], [3] andcombinations thereof are preferable, and the methods [2], [3] andcombinations thereof are more preferable.

The method in which a precursor of the resin (a) is allowed to react inan aqueous medium will be described in more detail.

The precursor (a0) of the resin (a) is not limited to any specific oneas long as it can be converted to the resin (a) by chemical reaction.For example, in a case where the resin (a) is a vinyl resin, examples ofthe precursor (a0) include the vinyl monomers mentioned above (which maybe used singly or in combination of two or more of them) and solutionsthereof.

In a case where the vinyl monomer is used as the precursor (a0),examples of the method for allowing the precursor (a0) to react toconvert it to the resin (a) include a method in which an oil phasecomprised of an oil-soluble initiator, the monomer, filler (b) and asolvent (s) (which will be described later) is dispersed and suspendedin water under the presence of a synthetic polymeric dispersant (h) tocarry out radical polymerization reaction by heating (that is, theso-called suspension polymerization method), and a method in which anoil phase comprised of the monomer and a solvent (s) is emulsified inwater containing an emulsifier and a water-soluble initiator to carryout radical polymerization reaction by heating (that is, the so-calledemulsion polymerization method).

As the oil-soluble initiator and the water-soluble initiator, peroxidepolymerization initiators, and azo polymerization initiators, and thelike can be used. A peroxide polymerization initiator may be used incombination with a reducing agent to form a redox polymerizationinitiator. Further, these initiators can be used in combination of twoor more of them.

Examples of the peroxide polymerization initiators include oil-solubleperoxide polymerization initiators and water-soluble peroxidepolymerization initiators.

As oil-soluble peroxide polymerization initiators,acetylcyclohexylsulfonyl peroxide, isobutylyl peroxide, diisopropylperoxydicarbonate, di-2-ethylhexyl peroxydicarbonate,2,4-dichlorobenzoyl peroxide, t-butyl peroxypivalate,3,5,5-trimethylhexanonyl peroxide, octanoyl peroxide, decanoyl peroxide,lauroyl peroxide, stearoly peroxide, propionitrile peroxide, succinicacid peroxide, acetyl peroxide, t-butyl peroxy-2-ethylhexanoate, benzoylperoxide, p-chlorobenzoylperoxide, t-butylperoxyisobutylate, t-butylperoxymaleic acid, t-butyl peroxylaurate, cyclohexanone peroxide,t-butyl peroxyisopropylcarbonate,2,5-dimethyl-2,5-dibenzoylperoxyhexane, t-butyl peroxyacetate, t-butylperoxybenzoate, diisobutyl diperoxyphthalate, methyl ethyl ketoneperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane,t-butylcumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide,diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, pinanehydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, cumene peroxide,and the like can be used.

As water-soluble peroxide polymerization initiators, hydrogen peroxide,peracetic acid, ammonium persulfate, potassium persulfate, sodiumpersulfate, and the like can be used.

Examples of the azo polymerization initiators include oil-soluble azopolymerization initiators and water-soluble azo polymerizationinitiators.

As oil-soluble azo polymerization initiators,2,2′-azobisisobutyronitrile, 1,1′-azobiscyclohexane-1-carbonytrile,2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile,2,2′-azobis-2,4-dimethylvaleronitrile,dimethyl-2,2′-azobis(2-methylpropionate),1,1′-azobis(1-acetoxy-1-phenylethane),2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), and the like can beused.

As water-soluble azo polymerization initiators, azobisamidinopropanesalt, azobiscyanovaleric acid (salt),2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], and the like canbe used.

As redox polymerization initiators, oil-soluble redox polymerizationinitiators and water-soluble redox polymerization initiators can bementioned.

Examples of the oil-soluble redox polymerization initiators includecombinations of oil-soluble peroxides such as hydroperoxides (e.g.,tert-butyl hydroxyperoxide and cumene hydroxyperoxide), dialkylperoxides (e.g., lauroyl peroxide), diacyl peroxides (e.g., benzoylperoxide), and the like and oil-soluble reducing agents such as tertiaryamines (e.g., triethylamine and tributylamine), naphthenic acid salts,mercaptans (e.g., mercaptoethanol and lauryl mercaptan), organic metalcompounds (e.g., triethylaluminum, triethylboron, and diethylzinc), andthe like.

Examples of the water-soluble redox polymerization initiators includecombinations of water-soluble peroxides such as persulfate salts (e.g.,potassium persulfate and ammonium persulfate), hydrogen peroxide,hydroperoxides (e.g., tert-butyl hydroxyperoxide and cumenehydroxyperoxide), and the like and water-soluble inorganic or organicreducing agents such as iron (II) salts, sodium bisulfite, alcohols, anddimethylaniline).

In a case where the resin (a) is a condensed resin (e.g., urethaneresin, an epoxy resin, or ester resin), a combination of a reactivegroup-containing prepolymer (a01) and a curing agent (a02) (which willbe described later) may also be used as the precursor (a0). Here, theword “reactive group” means a group capable of reacting with the curingagent (a02).

In this case, examples of a method of allowing the precursor (a0) toreact to form the resin particles (A) include the following methods (1)to (3):

(1) a method in which an oil phase containing the reactivegroup-containing prepolymer (a01), the curing agent (a02), the filler(b) and the solvent (s) is dispersed in an aqueous medium, and then thereactive group-containing prepolymer (a01) and the curing agent (a02)are allowed to react by heating to form the resin particles (A)comprising the resin (a);

(2) a method in which the reactive group-containing prepolymer (a01),the filler (b) and the solvent (s) are dispersed in an aqueous medium,and a water-soluble curing agent (a02) is added thereto to allow them toreact so as to form the resin particles (A) comprising the resin (a);and

(3) a method in which a dispersion containing the reactivegroup-containing prepolymer (a01), the filler (b) and the solvent (s)are dispersed in an aqueous medium to allow the reactivegroup-containing prepolymer (a01) to react with water to form the resinparticles (A) comprising the resin (a), the method being applicable to acase where the reactive group-containing prepolymer (a01) can be curedby the reaction with water.

Examples of a combination of the reactive group contained in thereactive group-containing prepolymer (a01) and the curing agent (a02)include the following combinations (1) and (2):

(1) a combination of a reactive group-containing prepolymer (a011)having a functional group capable of reacting with an activehydrogen-containing group and an active hydrogen-containing compound(a021); and

(2) a combination of a reactive group-containing prepolymer (a012)having an active hydrogen-containing group, and a curing agent (a022)having a functional group capable of reacting with an activehydrogen-containing group.

Among these combinations, the combination (1) is preferably used fromthe viewpoint of reaction rate in water.

Examples of a functional group capable of reacting with an activehydrogen-containing group include an isocyanate group, a blockedisosyanate group, an epoxy group, an acid anhydride group, and an acidhalide (e.g., acid chlorides and acid bromides) group.

Among them, an isocyanate group, a blocked isocyanate group, and anepoxy group are preferably used, more preferably an isocyanate group anda blocked isocyanate group.

In this regard, it is to be noted that the blocked isocyanate groupmeans an isocyanate group that is blocked with a blocking agent.

Examples of the blocking agent include well-known blocking agents suchas oximes (e.g., acetoxime, methyl isobutyl ketoxime, diethyl ketoxime,cyclopentanone oxime, cyclohexanone oxime and methyl ethyl ketoxime),lactams (e.g., γ-butyrolactam, ε-caprolactam, and γ-valerolactam),aliphatic alcohols having 1 to 20 carbon atoms (e.g., ethanol, methanol,and octanol), phenols (e.g., phenol, m-cresol, xylenol, andnonylphenol), activemethylene compounds (e.g., acetylacetone, ethylmalonate, and ethyl acetoacetate), basic nitrogen-containing compounds(e.g., N,N-diethylhydroxylamine, 2-hydroxypiridine, pyridine N-oxide,and 2-mercaptopyridine), and mixtures of two or more of them.

Among these blocking agents, oximes are preferably used, more preferablymethyl ethyl ketoxime.

As the skeleton of the reactive group-containing prepolymer (a01),polyethers, ester resins, epoxy resins, or urethane resins can be used.

Among them, ester resins, epoxy resins, and urethane resins arepreferably used, more preferably ester resins and urethane resins.

Examples of polyethers include polyethylene oxide, polypropylene oxide,polybutylene oxide, and polytetramethylene oxide.

Examples of ester resins include polycondensation products of the diols(11) and the dicarboxylic acids (13), and polylactones (e.g., thering-opening polymerization product of ε-caprolactone).

Examples of epoxy resins include addition-condensation products ofbisphenols (e.g., bisphenol A, bisphenol F, and bisphenol S) andepichlorohydrine.

Examples of urethane resins include polyaddition products of the diols(11) and the polyisocyanates (15), and polyaddition products of theester resins and the polyisocyanates (15).

A method of introducing the above mentioned reactive group into theester resin, the epoxy resin, or the urethane resin is not limited toany specific one, but examples of such a method include the followingmethods (1) and (2):

(1) a method in which one of components constituting the ester resin,the epoxy resin, or the urethane resin is used excessively to allow areactive group of the component to remain; and

(2) a method in which one of components constituting the ester resin,the epoxy resin, or the urethane resin is used excessively to allow afunctional group of the component to remain, and then the functionalgroup is further reacted with a compound having a functional group(reactive group) capable of reacting with the remaining functionalgroup.

According to the method (1), it is possible to obtain a hydroxylgroup-containing ester resin prepolymer, a carboxyl group-containingester resin prepolymer, an acid halide group-containing ester resinprepolymer, a hydroxyl group-containing epoxy resin prepolymer, an epoxygroup-containing epoxy resin prepolymer, a hydroxyl group-containingurethane resin prepolymer, and an isocyanate group-containing urethaneresin prepolymer, and the like.

For example, in the case of a hydroxyl group-containing ester resinprepolymer, the ratio between the components in the method (1), that is,the ratio between the alcohol components (e.g., the diols (11) and thepolyols (12)) and the carboxylic acid components (e.g., the dicarboxylicacids (13) and the polycarboxylic acids (14)) as expressed in terms ofthe equivalent ratio of hydroxyl group [OH] to carboxyl group [COOH],that is, the equivalent ratio [OH]/[COOH] is preferably in the range of2/1 to 1/1, more preferably in the range of 1.5/1 to 1/1, even morepreferably in the range of 1.3/1 to 1.02/1.

In each of the cases of a carboxyl group-containing ester resinprepolymer, an acid halide group-containing ester resin prepolymer, ahydroxyl group-containing urethane resin prepolymer, and an isocyanategroup-containing urethane resin prepolymer, components thereof aredifferent from those of the example case, but a preferred ratio betweenthe components is the same as described above.

According to the method (2), an isocyanate group-containing prepolymercan be obtained by allowing a prepolymer obtained by the method (1) toreact with polyisocyanate, a blocked isocyanate group-containingprepolymer can be obtained by allowing a prepolymer obtained by themethod (1) to react with blocked polyisocyanate, an epoxygroup-containing prepolymer can be obtained by allowing a prepolymerobtained by the method (1) to react with polyepoxide, and an acidanhydride group-containing prepolymer can be obtained by allowing aprepolymer obtained by the method (1) to react with a compound having 2or more acid anhydride groups.

For example, in the case of obtaining an isocyanate group-containingester resin prepolymer by allowing a hydroxyl group-containing esterresin to react with polyisocyanate according to the method (2), theamount of the compound having a reactive group to be used, that is, theratio between the hydroxyl group-containing ester resin andpolyisocyanate to be used as expressed in terms of the equivalent ratioof isocyanate group [NCO]/hydroxyl group [OH], that is, the equivalentratio [NCO]/[OH] is preferably in the range of 5/1 to 1/1, morepreferably in the range of 4/1 to 1.2/1, even more preferably in therange of 2.5/1 to 1.5/1.

In each of the cases of other prepolymers, components thereof aredifferent from those of the example case, but a preferred ratio betweenthe components is the same as described above.

The average number of the reactive group per molecule contained in thereactive group-containing prepolymer (a01) is preferably in the range of1 to 3, more preferably in the range of 1.5 to 3, even more preferablyin the range of 1.8 to 2.5. By setting the average number of thereactive group per molecule contained in the reactive group-containingprepolymer (a01) to a value within the above range, it is possible forthe resin (a) obtained by the reaction with the curing agent (a02) tohave high mechanical strength.

The Mn of the reactive group-containing prepolymer (a01) is preferablyin the range of 500 to 30,000. The upper limit is more preferably20,000, even more 10,000, the lower limit is more preferably 1,000, evenmore 2,000.

The Mw of the reactive group-containing prepolymer (a01) is preferablyin the range of 1,000 to 50,000. The upper limit is more preferably40,000, even more preferably 20,000, the lower limit is more preferably2,000, even more preferably 4,000.

As the active hydrogen group-containing compounds (a021), polyamineswhich may be blocked with removable compounds and polyols which may beblocked with removable compounds can be mentioned, in addition to theabove mentioned water, the diols (11), the polyols (12) having 3 to 6 ormore hydroxyl groups, the dicarboxylic acids (13), the polycarboxylicacids (14) having 3 to 4 or more carboxyl groups, the polyamines (16),and the polythiols (17).

Examples of a polyamine blocked with a removable compound includeketimine compounds obtained by dehydration between the polyamines (16)and ketones having 3 to 8 carbon atoms (e.g., acetone, methyl ethylketone, and methyl isobutyl ketone), aldimine compounds obtained bydehydration between the polyamines (16) and aldehyde compounds having 2to 8 carbon atom (e.g., formaldehyde and acetaldehyde), enaminecompounds obtainable from the polyamines (16) and ketones having 3 to 8carbon atoms or aldehydes having 2 to 8 carbon atoms, and oxazolidinecompounds.

Among these active hydrogen group-containing compounds (a021),polyamines which may be blocked, polyols which may be blocked, and waterare preferably used, more preferably polyamines which may be blocked andwater, even more preferably polyamines, ketimine compounds and water,most preferably 4,4′-diaminodiphenylmethane, xylylenediamine,isophoronediamine, ethylenediamine, diethylenetriamine,triethylenetetramine, ketimine compounds obtainable from thesepolyamines and ketones, and water.

When the resin particles (A) are produced, a reaction terminator (a02 s)may be used as necessary together with the active hydrogengroup-containing compound (a021). By using the reaction terminator (a02s) and the active hydrogen group-containing compound (a021) together ina certain ratio, it becomes easy to control the molecular weight of theresin (a) comprising the resin particles (A).

Examples of such a reaction terminator (a02 s) include monoamines having1 to 40 carbon atoms (e.g., diethylamine, dibutylamine, butylamine,laurylamine, monoethanolamine, and diethanolamine); blocked monoamineshaving 3 to 40 carbon atoms (e.g., ketimine compounds); monools having 1to 40 carbon atoms (e.g., methanol, ethanol, isopropanol, butanol, andphenol); monomercaptans having 2 to 40 carbon atoms (e.g.,butylmercaptan and laurylmercaptan) ; monoisocyanates having 5 to 40carbon atoms (e.g., butyl isocyanate, lauryl isocyanate, and phenylisocyanate); and monoepoxides having 2 to 40 carbon atoms (e.g., butylglycidyl ether).

In the combination (2) described above (that is, in the combination ofthe reactive group-containing prepolymer (a012) having an activehydrogen-containing group and the curing agent (a022) having afunctional group capable of reacting with an active hydrogen-containinggroup), examples of the active hydrogen-containing group contained inthe reactive group-containing prepolymer (a01) include an amino group,hydroxyl groups (an alcoholic hydroxyl group and a phenolic hydroxylgroup), a mercapto group, a carboxyl group, and organic groups obtainedby blocking these groups with removable compounds (e.g., ketones andaldehydes) (e.g., a ketimine-containing group, an aldimine-containinggroup, an oxazolidine-containing group, an enamine-containing group, anacetal-containing group, a ketal-containing group, athioacetal-containing group, and a thioketal-containing group).

Among these active hydrogen-containing groups, an amino group, hydroxylgroups, and organic groups obtained by blocking these groups withremovable compounds are preferably used, more preferably hydroxylgroups.

Examples of the curing agent (a022) having a functional group capable ofreacting with an active hydrogen-containing group include thepolyisocyanates (15), the polyepoxides (18), the dicarboxylic acids(13), the polycarboxylic acids (14), compounds having two or more acidanhydride groups, and compounds having two or more acid halide groups.

Among these curing agents (a022), the polyisocyanates and thepolyepoxides are preferably used, more preferably the polyisocyanates.

Examples of the compound having two or more acid anhydride groupsinclude a (co)polymer of pyromellitic anhydride and polymaleicanhydride, and the like.

Examples of the compound having two or more acid halide groups includeacid halides (e.g., acid chloride, acid bromide, and acid iodide) of thedicarboxylic acids (13) or the polycarboxylic acids (14).

When the resin particles (A) are produced, the reaction terminator (a02s) may be used as necessary together with the curing agent (a022) havinga functional group capable of reacting with an activehydrogen-containing group. By using the reaction terminator (a02 s) andthe curing agent (a022) together in a certain ratio, it becomes easy tocontrol the molecular weight of the resin (a) constituting the resinparticles (A).

The amount of the curing agent (a02) to be used as expressed in terms ofthe ratio [a01]/[a02] of the equivalent of the reactive group [a01] inthe reactive group-containing prepolymer (a01) to the equivalent of theactive hydrogen-containing group [a02] in the curing agent (a02) ispreferably in the range of 1/2 to 2/1, more preferably in the range of1.5/1 to 1/1.5, even more preferably in the range of 1.2/1 to 1/1.2.

In a case where water is used as the curing agent (a02), water isconsidered as a bifunctional active hydrogen-containing compound.

The length of time of reaction between the reactive group-containingprepolymer (a01) and the curing agent (a02) is selected according toreactivity that depends on the combination of the kind of reactive groupcontained in the prepolymer (a01) and the curing agent (a02), but ispreferably in the range of 10 minutes to 40 hours, more preferably inthe range of 30 minutes to 24 hours, even more preferably in the rangeof 30 minutes to 8 hours.

Further, the temperature of the reaction is preferably in the range of 0to 150° C., more preferably in the range of 50 to 120° C.

As necessary, a well-known catalyst can be used. Specifically, in thecase of the reaction between isocyanate and an activehydrogen-containing compound by way of example, dibutyltin laurate,dioctyltin laurate or the like can be used.

As the emulsifier and the dispersant used in the above-mentioned methods(1) to (4) for obtaining the aqueous dispersion containing the resinparticles (A), well-known surfactants (f) and synthetic polymericdispersants (h), and the like can be mentioned.

In a case where the surfactant (f) is used, the amount thereof to beused is preferably in the range of 0.0001 to 50%, more preferably in therange of 0.0005 to 0.4%, even more preferably in the range of 0.001 to0.3% with respect to the mass of the resin (a), the precursor thereof(a0) and the filler (b).

In a case where the synthetic polymeric dispersant (h) is used, theamount thereof to be used is preferably in the range of 0.005 to 0.6%,more preferably in the range of 0.01 to 0.4%, even more preferably inthe range of 0.02 to 0.3% with respect to the mass of the resin (a), theprecursor thereof (a0) and the filler (b).

Further, the plasticizer (k) or the like may be used as an emulsifierassistant or a dispersant assistant.

In a case where the plasticizer (k) is used, the amount thereof to beused is preferably in the range of 0.01 to 0.3%, more preferably in therange of 0.02 to 0.25%, even more preferably in the range of 0.03 to0.2% with respect to the mass of the resin (a) and the precursor thereof(a0).

The plasticizer (k) may be added as necessary to either water or theresin (a) at dispersion-emulsification.

As surfactants (f), anionic surfactants (f-1), cationic surfactants(f-2), amphoteric surfactants (f-3), and nonionic surfactants (f-4), andthe like can be used. In this regard, it is to be noted that thesesurfactants (f) can be used in combination of two or more of them. Inaddition to those exemplified blow, such surfactants as described inWO03/037964 can be used.

Examples of the anionic surfactant (f-1) include carboxylic acids orsalts thereof, sulfuric acid ester salts, salts of carboxymethylationproducts, sulfonic acid salts, and phosphoric acid ester salts.

As carboxylic acids or salts thereof, saturated or unsaturated fattyacids having 8 to 22 carbon atoms or salts thereof can be used, andexamples of such carboxylic acids include capric acid, lauric acid,myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid,ricinoleic acid, and mixtures of higher fatty acids obtained bysaponifying coconut oil, palm kernel oil, rice bran oil, beef tallow,and the like.

As the salts of these carboxylic acids, sodium salts, potassium salts,amine salts, ammonium salts, quaternary ammonium salts, and alkanolaminesalts (e.g., monoethanolamine salt, diethanolamine salt, andtriethanolamine salt), and the like can be mentioned.

As sulfuric acid ester salts, higher alcohol sulfuric acid ester salts(C₈-C₁₈ aliphatic alcohol sulfuric acid ester salts), higher alkyl ethersulfuric acid ester salts (C₈-C₁₈ aliphatic alcohol-E or PO (1 to 10mol) adduct sulfuric acid ester salts), sulfated oils (which areobtained by directly sulfating and neutralizing naturally-occurringunsaturated fats and oils having 12 to 50 carbon atoms or unsaturatedwaxes), sulfated fatty acid esters (which are obtained by sulfating andneutralizing lower alcohol (having 1 to 8 carbon atoms) esters ofunsaturated fatty acids (having 6 to 40 carbon atoms)), and sulfatedolefins (which are obtained by sulfating and neutralizing olefins having12 to 18 carbon atoms), and the like can be used.

As the salts, sodium salts, potassium salts, amine salts, ammoniumsalts, quaternary ammonium salts, alkanolamine salts (e.g.,monoethanolamine salt, diethanolamine salt, and triethanolamine salt),and the like can be mentioned.

Examples of the higher alcohol sulfuric acid ester salts include saltsof octyl alcohol sulfate, salts of lauryl alcohol sulfate, salts ofstearyl alcohol sulfate, sulfuric acid ester salts of alcohols (e.g.,“ALFOL 1214” which is a product of CONDEA) synthesized using a Zieglercatalyst, and sulfuric acid ester salts of alcohols (e.g., “Dobanol 23,25, 45” and “Diadol 115-L, 115-H, 135” which are products of MitsubishiChemical Corporation, “Tridecanol” which is a product of Kyowa HakkoKogyo Co., Ltd., and “Oxocol 1213, 1215, 1415” which are products ofNissan Chemical Industries, Ltd.) synthesized by oxo process.

Examples of the higher alkyl ether sulfuric acid ester salts includelauryl alcohol-EO (2 mol) adduct sulfuric acid ester salts, and octylalcohol-EO (3 mol) adduct sulfuric acid ester salts.

Examples of the sulfated oil include salts of sulfation products ofcastor oil, arachis oil, olive oil, rape oil, beef tallow, muttontallow, and the like.

Examples of the sulfated fatty acid ester include salts of sulfationproducts of butyl oleate, butyl ricinoleate, and the like.

An example of the sulfated olefins includes Teepol (which is a productof Shell Co.).

As salts of carboxymethylation products, salts of carboxymethylationproducts of aliphatic alcohols having 8 to 16 carbon atoms, salts ofcarboxymethylation products of C₈-C₁₆ aliphatic alcohol-EO or PO (1 to10 mol) adducts, and the like can be used.

Examples of the salts of carboxymethylation products of aliphaticalcohols include a sodium salt of carboxymethylated octyl alcohol, asodium salt of carboxymethylated decyl alcohol, a sodium salt ofcarboxymethylated lauryl alcohol, and a sodium salt of carboxymethylatedtridecanol.

Examples of the salts of carboxymethylation products of aliphaticalcohol-EO (1 to 10 mol) adducts include a sodium salt ofcarboxymethylation product of octyl alcohol-EO (3mol) adduct, a sodiumsalt of carboxymethylation product of lauryl alcohol-EO (4 mol) adduct,and a sodium salt of carboxymethylation product of Dobanol 23-EO (3 mol)adduct.

As sulfonic acid salts, alkylbenzene sulfonates, alkylnaphthalenesulfonates, sulfosuccinic acid diester salts, α-olefin sulfonates,IgeponT type, other sulfonates of aromatic ring-containing compounds,and the like can be used.

An example of the alkylbenzene sulfonates includes sodiumdodecylbenzensulfonate.

An example of the alkylnaphthalene sulfonates includes sodiumdodecylnaphthalenesulfonate.

An example of the sulfosuccinic acid diester salts includes sodiumdi-2-ethylhexyl sulfosuccinate.

Examples of the sulfonates of aromatic ring-containing compounds includealkylated diphenyl ether mono- or disulfonate and styrenated phenolsulfonate.

As phosphoric acid ester salts, higher alcohol phosphoric acid estersalts, higher alcohol-EO adduct phosphoric acid ester salts, and thelike can be used.

Examples of the higher alcohol phosphoric acid ester salts includelauryl alcohol phosphoric acid monoester disodium salt, and laurylalcohol phosphoric acid diester sodium salt.

An example of the higher alcohol-EO adduct phosphoric acid ester saltsincludes oleyl alcohol-EO (5 mol) adduct phosphoric acid monoesterdisodium salt.

As cationic surfactants (f-2), quaternary ammonium salt-typesurfactants, amine salt-type surfactants, and the like can be used.

The quaternary ammonium salt-type surfactants can be obtained by thereaction between tertiary amines having 3 to 40 carbon atoms andquaternizing agents (e.g., alkylating agents such as methyl chloride,methyl bromide, ethyl chloride, benzyl chloride, and dimethyl sulfate,and EO), and examples of such quaternary ammonium salt-type surfactantsinclude lauryltrimethylammonium chloride, dioctyldimethylammoniumbromide, stearyltrimethylammonium bromide, lauryldimethylbenzylammoniumchloride (benzalkonium chloride), cetylpyridinium chloride,polyoxyethylenetrimethylammonium chloride, andstearamidoethyldiethylmethylammonium methosulfate.

The amine salt-type surfactants can be obtained by neutralizing primaryto tertiary amines with inorganic acid (e.g., hydrochloric acid, nitricacid, sulfuric acid, hydrogen iodide, phosphoric acid, or perchloricacid) or organic acid (e.g., acetic acid, formic acid, oxalic acid,lactic acid, gluconic acid, adipic acid, alkylphosphoric acid having 2to 24 carbon atoms, malic acid, or citric acid).

Examples of primary amine salt-type surfactants include inorganic ororganic acid salts of aliphatic higher amines having 8 to 40 carbonatoms (e.g., higher amines such as laurylamine, stearylamine,hydrogenated beef tallow amine, and rosin amine), and C₈-C₄₀ higherfatty acid (e.g., stearic acid and oleic acid) salts of lower amineshaving 2 to 6 carbon atoms.

Examples of secondary amine salt-type surfactants include inorganic ororganic acid salts of aliphatic amine (having 4 to 40 carbon atoms)-EOadducts.

Examples of tertiary amine salt-type surfactants include inorganic ororganic acid salts of aliphatic amines having 4 to 40 carbon atoms(e.g., triethylamine, ethyldimethylamine, andN,N,N′,N′-tetramethylethylenediamine), aliphatic amines (having 2 to 40carbon atoms)-EO (2 or more mol) adducts, alicyclic amines having 6 to40 carbon atoms (e.g., N-methylpyrrolidine, N-methylpiperidine,N-methylhexamethyleneimine, N-methylmorpholine, and1,8-diazabicyclo(5,4,0)-7-undecene), nitrogen-containing heterocyclicaromatic amines having 5 to 30 carbon atoms (e.g.,4-dimetylaminopyridine, N-methylimidazole, and 4,4′-dipyridyl), andinorganic or organic acid salts of tertiary amines such astriethanolamine monostearate, stearamidoethyldiethylmethylethanolamine,and the like.

As amphoteric surfactants (f-3), carboxylic acid salt-type amphotericsurfactants, sulfuric acid ester salt-type amphoteric surfactants,sulfonic acid salt-type amphoteric surfactants, phosphoric acid estersalt-type amphoteric surfactants, and the like can be used.

As the carboxylic acid salt-type amphoteric surfactants, aminoacid-based amphoteric surfactants, betaine-type amphoteric surfactants,and imidazoline-type amphoteric surfactants, and the like can be used.The amino acid-type amphoteric surfactant is an amphoteric surfactanthaving an amino group and a carboxyl group in the molecule, and examplesof such amino acid-type amphoteric surfactant include compoundsrepresented by the general formula (2):[R—NH—(CH₂)_(n)—COO]_(m)M   (2)

wherein R represents a monovalent hydrocarbon group, n is 1 or 2, m is 1or 2, and M represents a hydrogen ion, an alkali metal ion, analkaline-earth metal ion, an ammonium cation, an amine cation, analkanolamine cation, or the like.

Examples of the amphoteric surfactants represented by the generalformula (2) include alkyl (having 6 to 40 carbon atoms) aminopropionicacid-type amphoteric surfactants (e.g., sodium stearylaminopropionateand sodium laurylaminopropionate) and alkyl (having 4 to 24 carbonatoms) aminoacetic acid-type amphoteric surfactants (e.g., sodiumlaurylaminoacetate).

The betaine-type amphoteric surfactant is an amphoteric surfactanthaving a quaternary ammonium salt-type cationic moiety and a carboxylicacid-type anionic moiety in the molecule, and examples of such abetaine-type amphoteric surfactant include alkyl (having 6 to 40 carbonatoms) dimethylbetaines (e.g., stearyldimethylaminoacetic acid betaineand lauryldimethylaminoacetic acid betaine), amido betaines having 6to40 carbon atoms (e.g., coco-fatty acid amidopropyl betaine), and alkyl(having 6 to 40 carbon atoms) dihydroxyalkyl (having 6 to 40 carbonatoms) betaines (e.g., lauryldihydroxyethyl betaine).

The imidazoline-type amphoteric surfactant is an amphoteric surfactanthaving a cationic moiety containing an imidazoline ring and a carboxylicacid-type anionic moiety, and an example of such an imidazoline-typeamphoteric surfactant includes2-undecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine.

As other amphoteric surfactants, glycine-type amphoteric surfactantssuch as sodium lauroyl glycine, sodium lauryl diaminoethylglycine,lauryldiaminoethylglycine hydrochloride, and dioctyldiaminoethylglycinehydrochloride, sulfobetaine-based amphoteric surfactants such aspentadecylsulfotaurine, sulfonic acid salt-type amphoteric surfactants,and phosphoric acid ester salt-type amphoteric surfactants, and the likecan be used.

As nonionic surfactants (f-4), AO adduct-type nonionic surfactants andpolyhydric alcohol-type nonionic surfactants, and the like can be used.

The AO adduct-type nonionic surfactants can be obtained by directlyadding AO (having 2 to 20 carbon atoms) to higher alcohols having 8 to40 carbon atoms, higher fatty acids having 8 to 40 carbon atoms oralkylamines having 8 to 40 carbon atoms, or by reacting higher fattyacids with polyalkylene glycols obtained by adding AO to glycol, or byadding AO to esterification products obtained by the reaction ofpolyhydric alcohols and higher fatty acids, or by adding AO to higherfatty acid amides.

Examples of AO include EO, PO, and BO.

Among them, EO, and a random or block adduct of EO and PO are preferablyused.

The number of mols of the AO to be added is preferably in the range of10 to 50 mols, and 50 to 100% of the added AO is preferably EO.

Examples of the AO adduct-type nonionic surfactants includeoxyalkylene(C₂-C₂₄) alkyl(C₈-C₄₀) ethers (e.g., octyl alcohol-EO (20mol) adduct, stearyl alcohol-EO (10 mol) adduct, oleyl alcohol-EO (5mol) adduct, and lauryl alcohol-EO (10 mol)/PO (20 mol) block adduct);polyoxyalkylene(C₂-C₂₄) higher fatty acid(C₈-C₄₀) esters (e.g., stearicacid-EO (10 mol) adduct and lauric acid-EO (10 mol) adduct); higherfatty acid(C₈-C₄₀) esters of polyoxyalkylene(C₂-C₂₄) polyhydricalcohols(C₃-C₄₀), (e.g., polyethylene glycol (Degree of polymerizationof 20) lauric acid diester, and polyethylene glycol (Degree ofpolymerization of 20) oleic acid diester; polyoxyalkylene(C₂-C₂₄)alykyl(C₈-C₄₀)phenyl ethers (e.g., nonylphenol-EO (4 mol) adduct,bisphenol A-EO (10 mol) adduct, and styrenated phenol-EO (20 mol)adduct); polyoxyalkylene(C₂-C₂₄) alkyl(C₈-C₄₀)amino ethers (e.g.,laurylamine-EO (10 mol) adduct and stearylamine-EO (10 mol) adduct); andpolyoxyalkylene(C₂-C₂₄) alkanolamides (in which amide (acylmoiety) has 8to24 carbon atoms) (e.g., hydroxypropyl oleylamide-EO (20 mol) adduct,and dihydroxyethyl laurylamide-EO (10 mol) adduct).

As polyhydric alcohol-type nonionic surfactants, polyhydric alcoholfatty acid esters, polyhydric alcohol fatty acid ester-AO adducts,polyhydric alcohol alkyl ethers, polyhydric alcohol alkyl ether-AOadducts, and the like can be used. Here, polyhydricalcohols have 3 to 24carbon atoms, fatty acids have 8 to 40 carbon atoms, and AO has 2 to 24carbon atoms.

Examples of the polyhydric alcohol fatty acid esters includepentaerythritol monolaurate, pentaerythritol monooleate, sorbitanmonolaurate, sorbitan monostearate, sorbitan dioleate, and sucrosemonostearate.

Examples of the polyhydric alcohol fatty acid ester-AO adducts includeethylene glycol monooleate-EO (10 mol) adduct, ethylene glycolmonostearate-EO (20 mol) adduct, trimethylolpropane monostearate-EO (20mol)/PO (10 mol) random adduct, sorbitan monolaurate-EO (10 mol) adduct,sorbitan distearate-EO (20 mol) adduct, and sorbitan dilaurate-EO (12mol)/PO (24 mol) random adduct.

Examples of the polyhydric alcohol alkyl ethers include pentaerythritolmonobutyl ether, pentaerythritol monolauryl ether, sorbitan monostearylether, methyl glycoside, and lauryl glycoside.

Examples of the polyhydric alcohol alkyl ether-AO adducts includesorbitan monostearyl ether-EO (10 mol) adduct, methyl glycoside-EO (20mol)/PO (10 mol) random adduct, and stearyl glycoside-EO (20 mol)/PO (20mol) random adduct.

Examples of the synthetic polymeric dispersants (h) include polyvinylalcohol, polyvinyl pyrrolidone, polyethylene glycol, polyethylene imine,and water-soluble urethane resins (e.g., reaction products ofpolyethylene glycol or polycaprolactone diol with polyisocyanates).

In the above methods of [1] to [4] for obtaining an aqueous dispersioncontaining resin particles (A), by using the method [3] or thecombination of the methods [2] and [3], a method of using organic fineparticles (A2) as at least a portion of a dead polymer of a resin (a),i.e., a method that involves adding the fine resin particles (A2), as adispersion stabilizer, to an aqueous medium (W), and carrying out, asnecessary, a reaction of a precursor (a0) in the an aqueous medium (W),can provide the resin particles (A) having a sharp particle sizedistribution. In other words, the above methods involve dispersing aresin (a) or its solvent solution or a precursor (a0) of the resin (a)or its solvent solution in an aqueous dispersion of a fine resinparticles (A2) comprising a resin (a2), carrying out, as necessary, thereaction of the precursor (a0), and then adsorbing the fine resinparticles (A2) onto the surfaces of resin particles (A1) having particlediameters larger than those of the fine resin particles (A2) when theresin particles (A) are formed, thereby preventing the resin particles(A1) or oil drops (A0) from sticking together in the oil-in-waterdispersion liquid (D1), and also rarely fragmenting the resin particles(A) in high shearing conditions. This converges the particle diametersof the resin particles (A) on a specified value, resulting the higheruniformity in particle diameter.

Therefore, the preferable properties of the fine resin particles (A2)include having an extent of strength of not being broken by shearing ina temperature during dispersion, hardly dissolving in water or swellingby water, or hardly dissolving in or swelling by a resin (a) or itssolvent solution or a precursor (a0) of a resin (a) or its solventsolution.

The resins (a2) constituting fine resin particles (A2) include, forexample, a vinyl resin, an urethane resin, an epoxy resin, an esterresin, a polyamide, a polyimide, a silicone resin, a fluorine resin, aphenol resin, a melamine resin, benzoguanamine based resin, an urearesin, an aniline resin, an ionomer resin, a polycarbonate, cellulose,mixtures thereof, and the like.

The method of preparing an aqueous dispersion of fine resin particles(A2) from a resin (a2) is not particularly limited, and the followingthe methods [1] to [8] are included.

-   [1] A method of directly producing an aqueous dispersion of fine    resin particles (A2) via polymerization reaction such as suspension    polymerization, emulsification polymerization, seed polymerization    or dispersion polymerization, using monomers as starting materials    for a vinyl resin.-   [2] A method of producing an aqueous dispersion of fine resin    particles (A2) that involves dispersing a precursor (monomer,    oligomer, or the like) or its solvent solution in an aqueous medium    in the presence of an appropriate dispersing agent, and heating the    resulting liquid or adding a curing agent thereto for curing, in the    case of polyaddition resins or condensed resins such as an ester    resin, a urethane resin, and an epoxy resin.-   [3] A method that involves dissolving an appropriate emulsifier in a    precursor (monomer, oligomer, or the like) or its solvent solution    (preferably a liquid, or may be liquefied by heating),    phase-inversion emulsifying the resulting solution by water    addition, then heating it or adding a curing agent thereto for    curing, in the case of polyaddition resins or condensed resins such    as an ester resin, a urethane resin, and an epoxy resin.-   [4] A method that involves grinding a resin prepared by    polymerization reaction (the polymerization reaction methods that    are allowable include any of addition polymerization, ring-opening    polymerization, polyaddition, addition condensation, condensation    polymerization, and the like) in advance by means of a granular    grinder such as a machine rotating type grinder or a jet type    grinder, obtaining resin particles by classification, and then    dispersing the resulting particles in water in the presence of an    appropriate dispersing agent.-   [5] A method that involves spraying in the form of a mist a resin    solution prepared by dissolving, in a solvent, a resin prepared by    polymerization reaction (the polymerization reaction methods that    are allowable include any of addition polymerization, ring-opening    polymerization, polyaddition, addition condensation, condensation    polymerization, and the like) in advance to obtain resin particles,    and subsequently dispersing the resin particles in water in the    presence of an appropriate dispersing agent.-   [6] A method that involves adding a poor solvent to a resin solution    prepared by dissolving, in a solvent, a resin prepared by    polymerization reaction (the polymerization reaction methods that    are allowable include any of addition polymerization, ring-opening    polymerization, polyaddition, addition condensation, condensation    polymerization, and the like) in advance, or cooling the resin    solution that is heat-dissolved in a solvent in advance to    precipitate the resin particles, obtaining the resin particles by    removal of the solvent, and then dispersing the resin particles in    water in the presence of an appropriate dispersing agent.-   [7] A method that involves dispersing, in an aqueous medium, a resin    solution prepared by dissolving, in a solvent, a resin prepared by    polymerization reaction (the polymerization reaction methods that    are allowable include any of addition polymerization, ring-opening    polymerization, polyaddition, addition condensation, condensation    polymerization, and the like) in advance in the presence of an    appropriate dispersing agent, and then subjecting the resulting    liquid to heating, pressure reduction or the like to remove the    solvent.-   [8] A method that involves dissolving an appropriate emulsifier in a    resin solution prepared by dissolving, in a solvent, a resin    prepared by polymerization reaction (the polymerization reaction    methods that are allowable include any of addition polymerization,    ring-opening polymerization, polyaddition, addition condensation,    condensation polymerization, and the like) in advance, and then    adding water thereto to phase-inversion emulsify the material.

The dispersing agent and emulsifier used in the methods [1] to [8] canutilize the above surfactant (f) used in the method of producing a resinparticle (A).

The particle diameter of a fine resin particle (A2) is normally smallerthan that of a resin particle (A1); the value of the particle diameterratio [volume average particle diameter of fine resin particles(A2)]/[volume average particle diameter of resin particles (A1)] ispreferably in the range of from 0.001 to 0.3 from the standpoint ofparticle diameter uniformity. If this particle diameter ratio is largerthan 0.3, the particle size distribution of the resulting resinparticles (A) tends to widen because fine resin particles (A2) do notefficiently adsorb on the surface of resin particles (A1).

The volume average particle diameter of fine resin particles (A2) can beappropriately controlled in the range of the above particle diameterratio so as to be a particle diameter suitable for obtaining a resinparticle (A) having a desirable particle diameter. For instance, ifresin particles (A) having a volume average particle diameter of 1 μmare needed, the volume average particle diameter of the fine resinparticles (A2) is preferably in the range of from 0.0005 to 0.3 μm,particularly preferably in the range of from0.001to 0.2 m; if resinparticles (A) having a volume average particle diameter of 10 μm areneeded, the volume average particle diameter of the fine resin particles(A2) is preferably in the range of from 0.005 to 3 μm, particularlypreferably in the range of from 0.05 to 2 μm; if resin particles (A)having a volume average particle diameter of 100 μm are needed, thevolume average particle diameter of the fine resin particles (A2) ispreferably in the range of from0.05 to 30 μm, particularly preferably inthe range of from 0.1 to 20 μm.

From the standpoints of particle diameter uniformity, powder flowabilityand storage stability, of resin particles (A), preferably 5% or more ofthe surface of a resin particle (A1) is covered with fine resinparticles (A2), more preferably 30% or more of the surface of a resinparticle (A1) is covered with fine resin particles (A2). The surfacecoverage can be determined from the image analysis of images obtained bya scanning electron microscope (SEM) according to the equation below:Surface coverage (%)=[area of a portion covered with a fine resinparticle (A2)/(area of a portion covered with a fine resin particle(A2)+area of a portion in which a resin particle (A1) is exposed)]×100

Examples of the solvents (s) used in the methods [1] to [4] to obtainthe aqueous dispersion containing resin particles (A) include aromatichydrocarbon solvents (e.g., toluene, xylene, ethylbenzene, andtetralin); aliphatic or alicyclic hydrocarbon solvents (e.g., n-hexane,n-heptane, mineral spirit, and cyclohexane); halogen-containing solvents(e.g., methyl chloride, methyl bromide, methyl iodide, methylenedichloride, carbon tetrachloride, trichloroethylene, andperchloroethylene); ester or ester ether solvents (e.g., ethyl acetate,butyl acetate, methoxybutyl acetate, methylcellosolve acetate, andethylcellosolve acetate); ether solvents (e.g., diethyl ether,tetrahydrofuran, dioxane, ethylcellosolve, butylcellosolve, andpropylene glycol monomethyl ether); ketone solvents (e.g., acetone,methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, andcyclohexanone); alcohol solvents (e.g., methanol, ethanol, n-propanol,isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, andbenzyl alcohol); amide solvents (e.g., dimethylformamide anddimethylacetamide); sulfoxide solvents (e.g., dimethylsulfoxide);heterocyclic compound solvents (e.g., N-methylpyrrolidone); and mixturesof two or more of them.

The solubility of the solvent (s) in water is preferably 80% or less,more preferably 70% or less, particularly preferably 50% or less. Thepresence of the solubility of the solvent (s) in the above ranges causesthe solvent (s) to be not instantaneously extracted into the water phasein the formation of the resin particle (A), so that an accumulationlayer (S0) in which the concentration of at least a portion (b*) of thefiller (b) is high is easy to form in an oil droplet (A0) in theoil-in-water dispersion (D1).

In addition, the boiling point of the solvent (s) is preferably 120° C.or less, more preferably 100° C. or less, particularly preferably from40 to 80° C., from the viewpoint of easy removal during solvent removal.

The plasticizer (k) to be used is not limited to any specific one, andthe above-mentioned plasticizers (k1) to (k5) and mixtures of two ormore of them can be used. A preferred range of the amount of theplasticizer to be used is the same as described above.

The amount of an aqueous medium to be used with respect to 100 parts bymass (hereinafter, “parts” means “parts by mass”) of the resin (a) ispreferably in the range of 50 to 2,000 parts, more preferably in therange of 100 to 1,000 parts, even more preferably in the range of 100 to500 parts. If the amount of an aqueous medium to be used is less thanabove lower limit, dispersibility of the resin (a) tends to be lowered.On the other hand, if the amount of an aqueous medium to be used exceedsthe above upper limit, economic problems tend to arise.

It should be noted that the aqueous medium is not limited to anyspecific one as long as it is a liquid containing water as an essentialcomponent. Examples of such an aqueous medium include water, aqueoussolutions of solvents, aqueous solutions of the surfactants (f), aqueoussolutions of the synthetic polymeric dispersants (h), and mixtures oftwo or more of them.

Examples of the solvents include, among the solvents (s) mentionedabove, ester or ester ether solvents, ether solvents, ketone solvents,alcohol solvents, amide solvents, sulfoxide solvents, heterocycliccompound solvents, and mixtures of two or more of them.

In a case where the aqueous medium contains such a solvent, the amountof the solvent contained in the aqueous medium is preferably in therange of 1 to 80% with respect to the mass of the aqueous medium. Theupper limit is more preferably 70%, even more preferably 30%, the lowerlimit is more preferably 2%, even more preferably 5%.

In a case where the surfactant (f) is used, the amount of the surfactant(f) contained in the aqueous medium is preferably in the range of 0.001to 0.3%, more preferably in the range of 0.005 to 0.2%, even morepreferably in the range of 0.01 to 0.15% with respect to the mass of theaqueous medium.

In a case where the synthetic polymeric dispersant (h) is used, theamount of the synthetic polymeric dispersant (h) contained in theaqueous medium is preferably in the range of 0.0001 to 0.2%, morepreferably in the range of 0.0002 to 0.15%, even more preferably in therange of 0.0005 to 0.1% with respect to the mass of the aqueous medium.

When the resin (a) and/or the precursor (a0) is dispersed in the aqueousmedium, the resin (a) and the precursor (a0) are preferably in the formof liquid or solution. In a case where the rein (a) and the precursor(a0) are solid at room temperatures, the resin (a) and the precursor(a0) may be dispersed at a temperature of the melting point thereof orhigher so that they can be dispersed in liquid form, or a solutionobtained by dissolving the resin (a) and the precursor (a0) in theabove-mentioned solvent (s) may be used.

In a case where the solvent (s) is used, a preferred solvent depends onthe kind of resin (a) and precursor (a0) to be used, but the differencein SP value between the resin (a) and the precursor (a0) is preferably 3or less.

The viscosities of the resin (a), the precursor (a0) and solventsolutions of these are preferably from 10 to 50,000 mPa·s, morepreferably from 100 to 30,000 mPa·s, particularly preferably from 200 to20,000 mPa·s, at 25° C. If they are within these ranges, unevenness onthe surface of the resin particle (A) is easy to form.

The temperature when the resin (a) and/or the precursor (a0) isdispersed in an aqueous medium is preferably from 0 to 150° C., morepreferably from 5 to 98° C., particularly preferably from 10 to 60° C.If the temperature exceeds 100° C., it indicates a temperature underpressurized conditions.

The dispersing apparatus when the resin (a) and/or the precursor (a0) ofthe resin, the filler (b) and, or solvent solutions of these aredispersed in an aqueous medium is not particularly limited, and examplesof the apparatus include batch emulsifiers such as a homogenizer(manufactured by IKA Japan K.K.), Polytron (manufactured by Kinematica),and TK Auto Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.),continuous emulsifiers such as Ebara Milder (manufactured by EbaraCorporation), TK Fillmix and TK Pipe Line Homomixer (manufactured byTokushu Kika Kogyo Co., Ltd.), Colloid Mill (manufactured by ShinkoPantech Co., Ltd.), a slasher and Trigonal wet pulverizer (manufacturedby Mitsui Miike Machinery Co., Ltd.), Cabitron (manufactured byEurotech, Ltd.), and Fine Flow Mill (manufactured by Pacific Machinery &Engineering Co., Ltd.), high-pressure emulsifiers such as Microfluidizer(manufactured by Mizuho Kogyo Co., Ltd.), Nanomizer (manufactured byNanomizer), and APV Gaulin (manufactured by Gaulin) membrane emulsifierssuch as a membrane emulsifier (manufactured by REICA), vibrationemulsifiers such as Vibro Mixer (manufactured by REICA), and ultrasonicemulsifiers such as an ultrasonic homogenizer (manufactured by BRANSON).Of these, from a view point of uniformity of particle size, APV Gaulin,a homogenizer, TK Auto Homomixer, Ebara Milder, TK Fillmix and TK PipeLine Homomixer are preferable.

In the present invention, for the formation of the outer shell layer (S)on the resin particle (A), at least a portion of the filler (b) ispreferably finely dispersed within the oil drop (A0) to increase thedispersion coefficient of the filler (b) because the filler (b) needs tobe dispersed onto the surface of the oil drop (A0) from the insidethereof. The method of dispersing at least a portion of the filler (b)is not particularly limited, well-known methods can be applied. Forinstance, the following the methods [1] to [6] and the methods combiningthese, and the like can be applied.

[1] A method that involves melt kneading the resin (a) and the filler(b), as necessary, in the presence of the solvent (s) and/or adispersing agent by means of a kneader, obtaining the master batch (m)in which the filler (b) is dispersed in the resin (a), and dispersingthe resulting material in the solvent (s).

[2] A method that involves dissolving or suspending the filler (b), asrequired, together with the resin (a) and/or the precursor (a0) of theresin (a) in the solvent (s), precipitating the particles in the liquidvia cooling crystallization, solvent crystallization or the like.

[3] A method that involves dissolving or suspending the filler (b), asrequired, together with the resin (a) and/or the precursor (a0) of theresin (a) in the solvent (s), precipitating the particles in the gasphase via spray drying or the like, and subsequently mixing anddispersing the precipitate in the solvent (s).

[4] A method that involves dissolving or suspending the filler (b), asrequired, together with the resin (a) and/or the precursor (a0) of theresin (a) in the solvent (s), mechanically wet pulverizing or shreddingthe resulting material with a disperser.

[5] A method that involves adding and mixing the filler (b) synthesizedin the solvent (s).

[6] A method that involves adding to the dispersion liquid (D0) anorganosol prepared by wet-treating the filler (b) dispersing in water bya surface treating agent (d) and subjecting to solvent replacement.

The kneaders used in the method [1] above include batch kneaders such asa roll mill and a universal mixer, a single or twin screw extrudingkneader, continuous kneaders such as a twin roll type kneader and atriple roll type kneader.

Examples of the method [2] above include a method of heat dissolving thefiller (b) in a solvent, and then cooling the resulting solution tocrystallize the particles of the filler (b), or a method of dissolvingthe filler (b) in a good solvent, and then adding the resulting solutionto a poor solvent to crystallize the particles of the filler (b). Inthese methods, a batch operation may be carried out by an agitationreaction vessel, a universal mixer, or the like, or a continuousoperation may be performed by the above high-pressure emulsifiers, whichare used for obtaining an aqueous dispersion containing resin particles(A), such as APV Gaulin, Nanomizer and a high-pressure homogenizer.

Examples of the method [3] above include a method that involves heatdissolving the filler (b) in a solvent, crystallizing the particles ofthe filler (b) in the gas phase by spray drying or the like, anddispersing the resulting particles in the solvent (s) by means of adisperser illustrated in the above method [2].

The dispersers used in the method [4] above can utilize media dispersers(i.e., beads mills) such as Dinomill (manufactured by ShinmaruEnterprises Corp.), Ultra-viscomill (manufactured by Imex Corp.) andPuremill (manufactured by Asada Iron Works Co., Ltd.), in addition tothe above emulsifiers used for obtaining an aqueous dispersioncontaining resin particles (A). Of these, preferred are Cabitron, EbaraMilder, Colloid Mill, Dinomill, Ultra-viscomill, and Puremill, from theview points of grindability and shredding properties of the filler (b).

Examples of the method [5] above include a method that involves addingas the filler (b) organic fine particles synthesized by dispersionpolymerization or precipitation polymerization in a solvent.

Examples of organosols of the filler (b) synthesized by a wet method inthe method [6] above include a hydrogel of a metal oxide synthesized bya hydrothermal synthesis method, a sol-gel method, or the like, and anorganosol obtained by the method that involves hydrophobing a dispersionliquid of organic fine particles obtained by emulsificationpolymerization, seed polymerization, suspension polymerization or thelike, by means of the above surface treating agent (d), and replacingthe water by the solvent (s) (preferably, methylethylketone, ethylacetate, or the like). Commercially available organosols prepared by theabove method (examples include organosilicasols [MEK-ST, MEK-ST-UP, andthe like] manufactured by Nissan Chemical Industries, Ltd.) may also beused.

From the viewpoint of dispersion stability, particularly the methods of[1], [4], [5] and [6] are preferable.

The content of the solvent (s) in the filler-containing dispersionliquid (D) is preferably from 20 to 80%, more preferably from 30 to 75%,particularly preferably from 40 to 70%. For the deformation of the shapeof the resin particle (A), the resin particle (A) needs to bevolume-shrunk, thus the content of the solvent (s) in the (D) ispreferably 20% or more.

The method of removing a solvent is not particularly limited, andwell-known methods are applicable; examples of the method that areapplicable include the methods [1] to [3] below, combination methodsthereof, and the like.

-   [1] A method of removing a solvent via heating and/or pressure    reduction in a generally employed vessel for solvent removal by    agitation, film evaporator or the like.-   [2] A method of performing air blowing on the surface of a solution,    or in a solution to remove a solvent.-   [3] A method of diluting a suspension of the filler-containing    dispersion liquid (D) and the aqueous medium (W) in water, and    extracting the solvent (s) in the continuous water phase.

In the method of [1], it is preferable that the temperature in heatingis a melting point (Tm) or below if the resin (a) is crystalline; if theresin (a) is non-crystalline, the temperature is the glass transitiontemperature (Tg) or below; the temperature is normally preferably 5° C.or less lower than Tm or Tg, more preferably 10° C. or less,particularly preferably 20° C. or less. The pressure reduction degree(i.e., gauge pressure) in pressure reduction is preferably −0.03 MPa orless, more preferably −0.05 MPa or less.

The method of [3] is a preferable method when the solvent (s) hassolubility to water. In general, the method of [1] is preferable.

When the speed of removing solvent is large, as the solvent of thesurface of the resin particle (A) is rapidly solvent-removed, so theviscosity difference between the inside and the surface of the resinparticle (A) becomes large, which in turn remarkably indicatesunevenness of the surface of the resin particle (A), thereby making theshape factor (SF-2) large. Accordingly, the selection of a method thatinvolves a larger solvent-removing speed can reduce the amount ofaddition of the filler (b).

The methods of removing an aqueous medium from the aqueous dispersioncontaining resin particles (A) that are applicable include the methods[1] to [3] below, the combinations thereof, and the like.

-   [1] A method of drying the aqueous medium under reduced pressure or    normal pressure.-   [2] A method of carrying out solid-liquid separation by means of a    centrifuge, a sparkler filter and/or a filter press, adding as    necessary, water or the like thereto and repeating solid-liquid    separation, and then drying the obtained solid.-   [3] A method of freezing an aqueous dispersion for drying (so-called    freeze drying).

In the methods of [1] and [2] above, drying can be carried out by usingwell-known equipments such as a fluidized-bed dryer, a vacuum dryer, ora circulation air dryer.

In addition, as appropriate, classification is performed by means of anair shift spreading machine, a sieve, or the like, and a specifiedparticle size distribution can be obtained.

The resin particle (A) of the present invention has a volume averageparticle diameter of from 0.1 to 300 μm, has the outer shell layer (S)of the filler (b*) adjacent to the surface of the resin particle (A)having a thickness of 0.01 μm or more and ½ or less of the radius of theinscribed circle of the resin particle (A), and further has a shapefactor (SF-2) of from 110 to 300. This provides a toner good in bladecleaning properties, low-temperature fixing properties, and anti-hotoffset properties. Moreover, the resin particle is excellent in maskingproperties and oil absorbance, and is suitable for a paint additive, acosmetics additive, a paper coating additive, an abrasive, a slushmolding material, a hot melt adhesive, a powder paint, other moldingmaterials, and the like.

EXAMPLES

The present invention will be further set forth in terms of Exampleshereinafter, but the invention is by no means limited thereto.

Production Example 1

Into a reaction vessel equipped with an agitation device and dehydratingdevice were placed 218 parts of a bisphenol A•EO (2 mol) adduct, 537parts of a bisphenol A•PO (3 mol) adduct, 213 parts of terephthalicacid, 47 parts of adipic acid, and 2 parts of dibutyltin oxide, and adehydration reaction was carried out under normal pressure at 230° C.for 5 hours, and then a dehydration reaction was performed under areduced pressure of 3 mmHg for 5 hours. After cooling to 180° C., and 43parts of trimellitic anhydride was placed thereto, and then a reactionwas carried out under normal pressure for 2 hours to yield [ester resin1]. [Ester resin 1] had a Tg of 44° C., a number average molecularweight of 2700, a weight average molecular weight of 6500, and an acidvalue of 25.

Production Example 2

Into a reaction vessel equipped with an agitation device and dehydratingdevice were placed 681 parts of a bisphenol A•EO (2 mol) adduct, 81parts of a bisphenol A•PO (2 mol) adduct, 275 parts of terephthalicacid, 7 parts of adipic acid, 22 parts of trimellitic anhydride and 2parts of dibutyltin oxide, and a dehydration reaction was carried outunder normal pressure at 230° C. for 5 hours, and then a dehydrationreaction was performed under a reduced pressure of 3 mmHg for 5 hours toobtain [ester resin 2]. [Ester resin 2] had a Tg of 54° C., a numberaverage molecular weight of 2200, a weight average molecular weight of9500, an acid value of 0.8 and a hydroxyl value of 53.

Production Example 3

Into an autoclave were placed 407 parts of [ester resin 2] obtained inProduction Example 2, 108 parts of IPDI and 485 parts of ethyl acetate,and a reaction was carried out in a sealed condition at 100° C. for 5hours to obtain [prepolymer solution 1] having an isocyante group at theterminal of the molecule. The NCO content of [prepolymer solution 1] was1.7%.

Production Example 4

Into a reaction vessel equipped with an agitation device,solvent-removing device and thermometer were placed 50 parts ofisophoronediamine and 300 parts of methyl ethyl ketone, and a reactionwas carried out at 50° C. for 5 hours, and then the resulting materialwas subjected to solvent removal to obtain [curing agent 1], a ketiminecompound. The total amine value of [curing agent 1] was 415.

Production Example 5

Into a reaction vessel fitted with a stirring rod and thermometer wereplaced 683 parts of water, 11 parts of a sodium salt of a sulfate esterof methacrylic acid ethylene oxide adduct (Eleminol RS-30, manufacturedby Sanyo Chemical Industries Ltd.), 139 parts of styrene, 138 parts ofmethacrylic acid, 184 parts of butyl acrylate, and 1 part of ammoniumpersulfate, and the resulting material was stirred at 400 revolutionsper minute for 15 minutes to obtain a white emulsion. The emulsion washeated to a system temperature of 75° C. and then reacted for 5 hours.Further, thereto was added 30 parts of a 1% aqueous ammonium persulfatesolution and the resulting mixture was matured at 75° C. for 5 hours toobtain an aqueous dispersion [fine particle dispersion liquid 1] of avinyl resin (a copolymer of styrene-methacrylic acid-butylmethacrylate-a sodium salt of a sulfate ester of methacrylic acid EOadduct). The volume average particle diameter of [fine particledispersion liquid 1] as determined by LA-920 was 0.15 μm.

Production Example 6

Into a vessel fitted with a stirring rod were placed 955 parts of water,15 parts of [fine particle dispersion liquid 1] obtained from ProductionExample5, and 30 parts of an aqueous solution of dodecyldiphenyl ethersodium disulfonate (Eleminol MON 7, manufactured by Sanyo ChemicalIndustries Ltd.) to obtain an opaque white liquid [water phase 1].

Production Example 7

[Water phase 2] was obtained as in <Production Example 6> with theexception that 15 parts of [fine particle dispersion liquid 1] was notadded.

Production Example 8

300 Parts of [ester resin 1] obtained in Production Example 1, 500 partsof copper phthalocyanine 15:3 (C. I. Pigment Blue 15:3) (mean primaryparticle diameter 25 nm) 150 parts of ester based pigment dispersingagent (Solsperse 24000SC, manufactured by Avecia Ltd.) and 50 parts of aphthalocyanine pigment derivative (Solsperse 5000, manufactured byAvecia Ltd.) were admixed with a Henschel mixer, and the resultingmixture was kneaded by means of a twin screw extruding kneader to obtain[master batch 1].

Production Example 9

150 Parts of [ester resin 1] obtained in Production Example 1, 50 partsof hydrophobic silica (Aerosil R974, mean primary particle diameter 12nm, manufactured by Nippon Aerosil Co., Ltd.), 5 parts ofbis(2-morphorinoethyl) ether, and 478 parts of ethyl acetate wereadmixed in an agitation mixing bath, and then the resulting mixture waswet dispersed by an Ultra-viscomill (manufactured by Imex Corp.) toobtain [silica dispersion liquid 1].

Production Example 10

To a reaction vessel fitted with a stirring rod and thermometer wereadded 50 parts of carnauba wax, 150 parts of [ester resin 1] and 470parts of ethyl acetate, and the resulting material was heated to 70° C.to melt the carnauba wax, and then cooled to 30° C. to crystallize thewax, thereby obtaining [wax dispersion liquid 1]. Further, [waxdispersion liquid 1] was wet dispersed by Ultra-viscomill (manufacturedby Imex Corp.) to obtain [wax dispersion liquid 2]. The solid content of[wax dispersion liquid 2] was 30%.

Production Example 11

Into an autoclave fitted with a stirring rod and thermometer was placed24 parts of xylene, and thereto were added dropwise at 170° C. over 3hours 2000 parts of a mixture of monomers of glycidylmethacrylate/methyl methacrylate/styrene/2-ethylhexyl acrylate (25% byweight/33% by weight/40% by weight/2% by weight) and 1 part of apolymerization catalyst and polymerized. The solution was gas removed atnormal pressure while being temperature increased to 180° C., and theoperation was switched to pressure reduction upon 180° C., and then gasremoval was performed under reduced pressure over two hours to obtain[vinyl resin 1]. [Vinyl resin 1] had a number average molecular weightof 10,500, a weight average molecular weight of 120,000 and a glasstransition temperature of 65° C.

Production Example 12

500 Parts of [ester resin 1] obtained in Production Example 1, and 500parts of copper phthalocyanine 15:3 (C. I. Pigment Blue 15;3; meanprimary particle diameter 25 nm) were admixed by means of Henschelmixer, and the resulting mixture was kneaded using a twin screwextruding kneader to obtain [master batch 2].

Comparative Production Example 1

[Silica dispersion liquid 2] was obtained as in Production Example 9with the exception that bis(2-morphorinoethyl)ether was not added.

Example 1

Into a beaker were placed 291 parts of [ester resin 1], 325 parts of[wax dispersion liquid 2], 213 parts of ethyl acetate, 119 parts of[prepolymer solution 1], 13 parts of [curing agent 1] and 39 parts of[master batch 1], and the resulting material was dissolved, admixed andhomogenized, and then 1500 parts of [water phase 1] was added thereto.The resulting material was dispersed at 25° C. for one minute using a TKHomomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at a revolutionnumber of 12000 rpm and further the solvent was removed using a filmevaporator under conditions of a pressure reduction degree of −0.05 MPa(gauge pressure), a temperature of 40° C. and a revolution number of 100rpm, for 30 minutes, to obtain an aqueous dispersion (D1).

100 Parts of the aqueous dispersion (D1) was centrifuged and further 60parts of water was added thereto and then centrifuged. The step of thesolid-liquid separation was repeated twice and the resulting materialwas dried at 35° C. for one hour to obtain a resin particle (P1). Thecharacteristic values of (P1) are indicated in Table 1.

Example 2

Into a beaker were placed 271 parts of [ester resin 1], 330 parts of[wax dispersion liquid 2], 39 parts of [master batch 2], 142 parts ofethyl acetate, 116 parts of [prepolymer 1], 13 parts of [curing agent 1]and 86 parts of organosilica sol (MEK-ST-UP, solid content 20%, meanprimary particle diameter 15 nm; manufactured by Nissan ChemicalIndustries, Ltd.), and the resulting material was dissolved, admixed andhomogenized, and then 1500 parts of [water phase 1] was added thereto.The resulting material was dispersed at 25° C. for one minute using a TKHomomixer at a revolution number of 12000 rpm and further the solventwas removed using a film evaporator under conditions of a pressurereduction degree of −0.05 MPa (gauge pressure), a temperature of 40° C.and a revolution number of 100 rpm, for 30 minutes, to obtain an aqueousdispersion (D2).

100 Parts of (D2) was centrifuged and further 60 parts of water wasadded thereto and then centrifuged. The step of the solid-liquidseparation was repeated twice and the resulting material was dried at35° C. for one hour to obtain a resin particle (P2). The characteristicvalues of (P2) were indicated in Table 1, a SEM image in FIG. 2, and aTEM image in FIG. 3. Silica alone was accumulated on the surface to formthe outer shell layer (in FIG. 3, the condition is judged from theappearance of the particle contour portion being a dark belt shape.),whereby the appearance of the resin particle surface being deformedunevenly (in FIG. 2, the appearance is seen from the particle lookinglike a “umeboshi (pickled plum) shape.” which means a plum having unevensurface due to dehydration-shrinkage.) was observed.

Example 3

In <Example 2> above, 115 parts of MEK-ST (solid content 30%, meanprimary particle diameter 15 nm; manufactured by Nissan ChemicalIndustries, Ltd.) in place of 86 parts of MEK-ST-UP was changed, and anaqueous dispersion (D3) and a resin particle (P3) were obtained in asimilar manner. The characteristic values of (P3) were shown in Table 1.

Example 4

Into a beaker were placed 223 parts of [ester resin 1], 324 parts of[wax dispersion liquid 2], 39 parts of [master batch 2], 54 parts ofethyl acetate, 114 parts of [prepolymer 1], 13 parts of [curing agent 1]and 231 parts of [silica dispersion liquid 1], and the resultingmaterial was dissolved, admixed and homogenized, and then 1500 parts of[water phase 1] was added thereto. The resulting material was dispersedat 25° C. for one minute using a TK Homomixer at a revolution number of12000 rpm and further the solvent was removed using a film evaporatorunder conditions of a pressure reduction degree of −0.05 MPa (gaugepressure), a temperature of 40° C. and a revolution number of 100 rpm,for 30 minutes, to obtain an aqueous dispersion (D4).

100 Parts of (D4) was centrifuged and further 60 parts of water wasadded thereto and then centrifuged. The step of the solid-liquidseparation was repeated twice and the resulting material was dried at35° C. for one hour to obtain a resin particle (P4). The characteristicvalues of (P4) were indicated in Table 1.

Example 5

In <Example 4> above, [ester resin 1] was changed to [vinyl resin 1],and an aqueous dispersion (D5) and a resin particle (P5) were obtainedin a similar manner. The characteristic values of (P5) were shown inTable 1.

Comparative Example 1

An aqueous dispersion (CD1) and a resin particle (CP1) were obtained asin Example 2 with the exception that the organosilica sol was not added.The characteristic values of (CP1) were indicated in Table 1, and a SEMimage was indicated in FIG. 4. FIG. 4 shows that (CP1) is a truespherical particle.

Comparative Example 2

In <Example 5> above, [silica dispersion liquid 2] was used in place of[silica dispersion liquid 1], and an aqueous dispersion (CD2) and aresin particle (CP2) were obtained in a similar manner. Thecharacteristic values of (CP2) were shown in Table 1.

Comparative Example 3

An aqueous dispersion (CD3) and a resin particle (CP3) were obtained asin <Example 1>, with the exception that [master batch 2] was used inplace of [master batch 1]. The characteristic values of (CP3) were shownin Table 1.

To the resin particles (P1) to (P5) and (CP1) to (CP3) obtained inExamples and Comparative Examples above, 1 part of hydrophobic silicaparticles based on 100 parts of resin particles are added, and theresulting materials were admixed by means of a Henschel mixer to obtainrespective toners (T1) to (T5) and (CT1) to (CT3).

Developers were prepared that comprise 5% of the toners obtained aboveand 95% of copper-zinc ferrite carriers having an average particlediameter of 40 μm, coated with silicone resin, and paper sheets of an A4size were continuously printed by means of imagio Neo 450 manufacturedby Ricoh, which can print the 45 paper sheets per minute, and evaluatedaccording to the criteria below. The results were shown in Table 1.

(a) Fixing Properties

The amount of a toner was adjusted such that a toner of 1.0±0.1 mg/cm²was developed on transfer paper (Type 6200, manufactured by Ricoh) witha solid image, and the adjustment was performed such that thetemperature of the fixing belt was changeable, and then the minimum andmaximum temperature values that did not cause offset were determined. Inaddition, the fixing roll temperature in which the residue percentage ofthe image density after the fixed image thus obtained was rubbed with apad was 70% or more was defined as the lower limit of fixingtemperature.

(b) Cleaning Properties

A remaining toner after transfer on a photoreceptor that passed throughthe cleaning step was moved to a white paper sheet with Scotch tape(manufactured by 3M Japan); the sheet density was determined by means ofa Macbeth Reflection Densitometer RD514 Model. A toner having a densityof 0.01 or less relative to the blank density was determined to be ∘(good) and a toner of a density exceeding the value was determined to bex (no good). The evaluation was carried out after 5000 sheets wereprinted.

TABLE 1 Example Comparative Example 1 2 3 4 5 1 2 3 Resin particle (A)P1 P2 P3 P4 P5 CP1 CP2 CP3 Toner T1 T2 T3 T4 T5 CT1 CT2 CT3 Kind offiller (b*) C.I. Pigment MEK-ST-U MEK-ST Aerosil Aerosil None AerosilC.I. Pigment Blue 15:3 P R974 R974 R974 Blue 15:3 Content [wt %] offiller 4 3.5 7 3.5 3.5 0 3.5 4 (b*) in resin particle (A) Volume average4.6 5.3 5.1 5.3 5.5 5.2 5.5 5.4 particle diameter [μm] of resin particle(A) Dv/Dn of resin particle (A) 1.21 1.13 1.15 1.22 1.14 1.11 1.13 1.14Thickness [μm] of outer 0.05 0.03 0.03 0.02 0.03 0 0 0 shell layer (S)Shape factor (SF-2) of 132 137 136 135 134 102 105 108 resin particle(A) Center line average 0.3 0.1 0.1 0.1 0.1 0 0 0 surface roughness [μm]of resin particle (A) Blade cleaning properties ∘ ∘ ∘ ∘ ∘ x x x Lowerlimit of fixing 135 140 135 140 150 135 140 135 temperature [° C.] Upperlimit of fixing >210 >210 >210 >210 >210 >210 >210 >210 temperature [°C.]

Example 6

Into a beaker were placed 365 parts of [ester resin 1], 426 parts ofethyl acetate, 147 parts of [prepolymer solution 1], 16 parts of [curingagent 1] and 45 parts of [master batch 1], and the resulting materialwas dissolved, admixed and homogenized, and then 1500 parts of [waterphase 1] was added thereto. The resulting material was dispersed at 25°C. for one minute using a TK Homomixer (manufactured by Tokushu KikaKogyo Co., Ltd.) at a revolution number of 12000 rpm and further thesolvent was removed using a film evaporator under conditions of apressure reduction degree of −0.05 MPa (gauge pressure), a temperatureof 40° C. and a revolution number of 100 rpm, for 30 minutes, to obtainan aqueous dispersion (D6).

100 Parts of (D6) was centrifuged and further 60 parts of water wasadded thereto and then centrifuged. The step of the solid-liquidseparation was repeated twice and the resulting material was dried at35° C. for one hour to obtain a resin particle (P6). The characteristicvalues of (P6) were indicated in Table 2.

Example 7

Into a beaker were placed 388 parts of [ester resin 1], 344 parts ofethyl acetate, 151 parts of [prepolymer 1], 17 parts of [curing agent 1]and 101 parts of organosilica sol (MEK-ST-UP, solid content 20%;manufactured by Nissan Chemical Industries, Ltd.), and the resultingmaterial was dissolved, admixed and homogenized, and then 1500 parts of[water phase 1] was added thereto. The resulting material was dispersedat 25° C. for one minute using a TK Homomixer at a revolution number of12000 rpm and further the solvent was removed using a film evaporatorunder conditions of a pressure reduction degree of −0.05 MPa (gaugepressure), a temperature of 40° C. and a revolution number of 100 rpm,for 30 minutes, to obtain an aqueous dispersion (D7). 100 Parts of (D7)was centrifuged and further 60 parts of water was added thereto and thencentrifuged. The step of the solid-liquid separation was repeated twiceand the resulting material was dried at 35° C. for one hour to obtain aresin particle (P7). The characteristic values of (P7) were indicated inTable 2, a SEM image in FIG. 5, and a TEM image in FIG. 6. Silica alonewas accumulated on the surface to form the outer shell layer (in FIG. 6,the condition is judged from the appearance of the particle contourportion being a dark belt shape.), whereby the appearance of the resinparticle surface being deformed unevenly (in FIG. 5, the appearance isseen from the particle looking like a “umeboshi (pickled plum) shape.”which means a plum having uneven surface due to dehydration-shrinkage.)was observed.

Example 8

In <Example 7> above, 135 parts of MEK-ST (solid content 30%;manufactured by Nissan Chemical Industries, Ltd.) was employed in placeof 67 parts of MEK-ST-UP (manufactured by Nissan Chemical Industries,Ltd.), and an aqueous dispersion (D8) and a resin particle (P8) wereobtained in a similar manner. The characteristic values of (P8) wereshown in Table 2.

Example 9

Into a beaker were placed 323 parts of [ester resin 1], 233 parts ofethyl acetate, 149 parts of [prepolymer 1], 17 parts of [curing agent 1]and 276 parts of [silica dispersion liquid 1], and the resultingmaterial was dissolved, admixed and homogenized, and then 1500 parts of[water phase 1] was added thereto. The resulting material was dispersedat 25° C. for one minute using a TK Homomixer at a revolution number of12000 rpm and further the solvent was removed using a film evaporatorunder conditions of a pressure reduction degree of −0.05 MPa (gaugepressure), a temperature of 40° C. and a revolution number of 100 rpm,for 30 minutes, to obtain an aqueous dispersion (D9). 100 Parts of (D9)was centrifuged and further 60 parts of water was added thereto and thencentrifuged. The step of the solid-liquid separation was repeated twiceand the resulting material was dried at 35° C. for one hour to obtain aresin particle (P9). The characteristic values of (P9) were indicated inTable 2.

Example 10

Into a beaker were placed 483 parts of poly methyl methacrylate(Sumipex-BMHO, manufactured by Sumitomo Chemical Co., Ltd.), 430 partsof ethyl acetate, and 87.5 parts of organosilica sol (MEK-ST-UP, solidcontent 20%; manufactured by Nissan Chemical Industries, Ltd.), and theresulting material was dissolved, admixed and homogenized, and then 1500parts of [water phase 2] was added thereto. The resulting material wasdispersed at 25° C. for one minute using a TK Homomixer at a revolutionnumber of 12000 rpm and further the solvent was removed using a filmevaporator under conditions of a pressure reduction degree of −0.05 MPa(gauge pressure), a temperature of 40° C. and a revolution number of 100rpm, for 30 minutes, to obtain an aqueous dispersion (D10).

100 Parts of (D10) was centrifuged and further 60 parts of water wasadded thereto and then centrifuged. The step of the solid-liquidseparation was repeated twice and the resulting material was dried at35° C. for one hour to obtain a resin particle (P10). The characteristicvalues of (P10) were indicated in Table 2.

Comparative Example 4

An aqueous dispersion (CD4) and a resin particle (CP4) were obtained asin Example 7 with the exception that the organosilica sol was not added.The characteristic values of (CP4) were indicated in Table 2, and a SEMimage was indicated in FIG. 7. FIG. 7 shows that (CP4) is a truespherical particle.

Comparative Example 5

In <Example 10> above, [silica dispersion liquid 2] was used in place of[silica dispersion liquid 1], and an aqueous dispersion (CD5) and aresin particle (CP5) were obtained in a similar manner. Thecharacteristic values of (CP5) were shown in Table 2.

Comparative Example 6

An aqueous dispersion (CD6) and a resin particle (CP6) were obtained asin Example 6, with the exception that [master batch 2] was used in placeof [master batch 1] in Example 6. The characteristic values of (CP6)were shown in Table 2.

[Masking Rate]

The above resin particles (P6) to (P10) and (CP4 to CP6) are mixed withan acrylic paint [manufactured by Shinto Paint Co., Ltd.: Shinto Acryl#6000] such that the ratio of the solid content of the resin to that ofthe paint is 1:1. Next, each of these was applied to a black ABS resinplate in such a way that the dried film thickness was 100 μm, and thenthe resulting plate was dried at 80° C. for 30 minutes. The gloss of theglossiness sample surface was measured using a gloss meter (manufacturedby Horiba, Ltd.) at an incidence (light receiving) angle of 60°. In thiscase, the gloss of a coated film of an acrylic paint, i.e., a binder, is80%. The masking rate was determined by use of an applicator having amasking rate clearance of 100 μm in accordance with JIS K5400.

TABLE 2 Example Comparative Example 6 7 8 9 10 4 5 6 Resin particle (A)P6 P7 P8 P9 P10 CP4 CP5 CP6 Kind of filler (b*) C.I. Pigment MEK-ST-UMEK-ST Aerosil MEK-ST-U None Aerosil C.I. Pigment Blue 15:3 P R974 PR974 Blue 15:3 Content [wt %] of filler 4 3.5 7 — 3.5 0 3.5 4 (b*) inresin particle (A) Volume average 4.1 3.8 5.6 8.9 23.5 4.6 7.2 4.5particle diameter [μm] of resin particle (A) Dv/Dn of resin particle (A)1.25 1.16 1.21 1.53 1.91 1.24 1.37 1.31 Thickness [μm] of outer 0.070.03 0.03 0.04 0.01 0 0 0 shell layer (S) Shape factor (SF-2) of 154 128127 124 141 104 108 108 resin particle (A) Center line average 0.3 0.10.1 0.1 0.2 0 0 0 surface roughness [μm] of resin particle (A) Maskingrate [%] 100% 100% 100% 100% 100% 85% 91% 93%

INDUSTRIAL APPLICABILITY

As a resin particle of the present invention has the above effects, sois useful as a toner resin, a paint additive, a cosmetics additive, apaper coating additive, a slush molding material, a powder paint, and anabrasive.

1. A resin particle comprising a resin (a) and a filler (b) contained inthe particle; characterized in that the particle has a volume averageparticle diameter of from 0.1 to 300 μm and a shape factor (SF-2) offrom 110 to 300, the particle having an outer shell layer (S) comprisingat least a portion of the filler (b), the layer (S) having a thicknessof at least 0.01 μm and the thickness being ½ or less of the radius ofthe maximum inscribed circle of the cross section of the particle,wherein a part of the resin (a) is present on the surface of the resinparticle.
 2. The resin particle according to claim 1, wherein the ratioof the center line average surface roughness to the volume averageparticle diameter is from 0.001 to 0.1.
 3. The resin particle accordingto claim 1, wherein the ratio of the volume average particle diameter tothe number average particle diameter is from 1.0 to 2.0.
 4. The resinparticle according to claim 1, wherein the resin particle comprises from0.01 to 50% by mass of the filler (b) and from 0.01 to 20% by mass ofthe filler (b) constituting the layer (S).
 5. The resin particleaccording to claim 1, wherein the layer (S) comprises a filler (b) aprimary particle thereof having a volume average particle diameter offrom 0.001 to 3 μm.
 6. The resin particle according to claim 5,whereinthe ratio of the volume average particle diameter of the primaryparticle of the filler (b) to the volume average particle diameter ofthe resin particle is 0.1 or less.
 7. The resin particle according toclaim 1, wherein the filler (b) comprises an inorganic filler (b1), anorganic filler (b2), or the combination of an inorganic filler (b1) andan organic filler (b2), the inorganic filler (b1) being selected fromthe group consisting of metal oxides, metal hydroxides, metalcarbonates, metal sulfates, metal silicates, metal nitrides, metalphosphates, metal borates, metal titanates, metal sulfates, and carbons,the organic filler (b2) being selected from the group consisting ofurethane resins, epoxy resins, vinyl resins, ester resins, melamineresins, benzoguanamine resins, fluorine resins, silicone resins, azopigments, phthalocyanine pigments, condensation polycyclic pigments,coloring lake pigments and organic waxes.
 8. The resin particleaccording to claim 1, wherein the layer (S) comprises the filler (b)treated with a surface treating agent (d) selected from the groupconsisting of a silane coupling agent, a titanate coupling agent, analuminate coupling agent, and a tertiary amine compound.
 9. The resinparticle according to claim 1, wherein the resin (a) is one or morekinds of resins selected from the group consisting of urethane resins,epoxy resins, vinyl resins and ester resins.
 10. The resin particleaccording to claim 1, wherein the resin particle comprises a resinparticle (A1) having a particle diameter larger than that of a fineresin particle (A2), at least a portion of the surface of the resinparticle (A1) being covered with the layer of the fine resin particle(A2) comprising one or more kinds of resins selected from the groupconsisting of urethane resins, epoxy resins, vinyl resins and esterresins.
 11. The resin particle according to claim 10, wherein at least5% of the surface of the resin particle (A1) is covered with the fineresin particle (A2).
 12. The resin particle according to claim 10,wherein the fine resin particle (A2) has a volume average particlediameter such that the ratio of the volume average particle diameter ofthe fine resin particle (A2) to the volume average particle diameter ofthe resin particle (A1) is from 0.001 to 0.3.
 13. A process of producinga resin particle (A) of claim 1, comprising: (1) dispersing in anaqueous medium (W) a filler-containing dispersion liquid (D) produced bydispersing a filler (b) in a dispersion liquid (D0) comprising a resin(a) and/or its precursor (a0) in a solvent (s), forming an oil-in-waterdispersion liquid (D1), thereby forming in an oil drop (A0) anaccumulated layer (S0) comprising at least a portion of the filler (b),and (2) removing the solvent of the oil-in-water dispersion liquid (D1)to obtain a resin particle (A).
 14. The process of production accordingto claim 13, wherein the content of the solvent (s) in the dispersionliquid (D) is from 20 to 80% by mass.
 15. The process of productionaccording to claim 13, wherein the dispersion liquid (D) is obtained bydispersing in the solvent (s) a master batch (m) obtained by meltkneading at least a portion of the resin (a) and the filler (b), asnecessary, in the presence of a solvent and/or a dispersing agent. 16.The process of production according to claim 13, wherein the dispersionliquid (D) is obtained by dispersing an organosol of at least a portionof the filler (b) synthesized by a wet method in the dispersion liquid(D0).
 17. The process of production according to claim 13, wherein atleast a portion of the filler (b) is pulverized or shredded in thesolvent (s) in the presence or absence of the resin (a) and/or itsprecursor (a0).
 18. The process of production according to claim 13,wherein the precursor (a0) comprises a prepolymer (a01) having at leastone reactive group and a curing agent (a02) reactive to the reactivegroup.
 19. The process of production according to claim 18, wherein thereactive group is selected from the group consisting of an isocyanategroup, a blocked isocyanate group and an epoxy group.
 20. The process ofproduction according to claim 13, wherein the dispersion solution (D) isdispersed in the aqueous medium (W) containing a fine resin particle(A2) comprising one or more species selected from the group consistingof a urethane resin, an epoxy resin, a vinyl resin and an ester resin.21. Use of the resin particle of claim 1 as a toner resin, a paintadditive, a cosmetics additive, a paper coating additive, a slushmolding material, a powder paint, or an abrasive.